Thiadiazole derivatives and herbicide compositions containing the same

ABSTRACT

Thiadiazole derivatives with excellent herbicidal effectiveness, wide herbicidal spectrum and excellent selectivity are disclosed. The thiadiazole derivatives are represented by one of the formula [I]-[IV].    &lt;IMAGE&gt;  [I]   &lt;IMAGE&gt;  [II]   &lt;IMAGE&gt;  [III]   &lt;IMAGE&gt;  [IV]

This is a Division of application Ser. No. 08/027,579, filed Mar. 5, 1993, pending which is a continuation of Ser. No. 07/633,348, filed Dec. 27, 1990, abandoned; which is a continuation-in-part of Ser. No. 07/570,638, filed Aug. 22, 1990, now abandoned.

BACKGROUND OF THE INVENTION

I. Field of the Invention

The present invention relates to thiadiazol derivatives and herbicide compositions containing the same.

II. Description of the Related Art

A number of herbicides have been developed and used. However, in general, the conventional herbicides have a problem in that their herbicidal effectiveness is unsatisfactory, herbicidal spectrum is narrow or crops are damaged by the herbicides.

It is known that 2,1,3-benzothiadiazole derivatives as well as 1,2,4- and 1,3,4- thiadiazole derivatives have herbicidal activities. However, it has not been known that 1,2,5-thiadiazole derivatives have herbicidal activities.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel compound which exhibits high herbicidal activities and which does not damage the crops, as well as a herbicide composition containing the novel compound as an effective ingredient.

The present inventors intensively studied to find that specific 1,2,5-thiadiazole derivatives exhibit high herbicidal activities against wide variety of weeds while they do not substantially damage the crops, to complete the present invention.

That is, the present invention provides a thiadiazole derivative represented by the formula [I] ##STR2## [wherein Y represents oxygen or sulfur; X represents hydrogen, halogen, lower alkyl, lower haloalkyl, lower alkoxy, hydroxy or nitro; V and Z, the same or different, represent halogen, lower alkyl, lower haloalkyl, lower alkoxy, hydroxy or nitro; A represents hydrogen, lower alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl which may be substituted with alkoxy, alkylthioalkyl --SO₂ R¹ (wherein R¹ represents lower alkyl which may be substituted with halogen, phenyl which may be substituted with lower alkyl, or amino which is substituted with lower alkyl), ##STR3## (wherein n represents 0 or 1, B represents CH or nitrogen, R² and R³, the same or different, represent hydrogen, halogen, lower alkoxy, nitro or lower alkyl which may be substituted with halogen), --SiR⁴ R⁵ R⁶ (wherein R⁴, R⁵ and R⁶, the same or different, represent lower alkyl), --CHR⁷ COR⁸ (wherein R⁷ represents hydrogen or lower alkyl, R⁸ represents hydroxy or amino which may be substituted with lower alkyl and/or with phenyl), --C(═W)OR⁹ (wherein W represents oxygen or sulfur, R⁹ represents alkyl which may be substituted with halogen; alkoxyalkyl, benzyl, phenyl, tetrahydrofurfuryl or alkylideneamino), --COR¹⁰ (wherein R¹⁰ represents lower alkyl; cycloalkyl; or phenyl which may be substituted with halogen, lower alkyl, lower haloalkyl, lower alkoxy, nitro or with cyano; --C(═W)NR¹¹ R¹² (wherein W represents oxygen or sulfur, R¹¹ and R¹², the same or different, represent hydrogen, lower alkyl, cycloalkyl, lower alkoxy, alkoxyalkyl, phenyl which may be substituted with alkoxy, ##STR4## (wherein R¹³ and R¹⁴, the same or different, represent hydrogen, halogen, lower alkyl or lower alkoxy)), or R¹¹ and R¹² cooperatively form ##STR5## (wherein E¹ represents --CH₂ -- or oxygen, m represents 0 or 1, R¹⁵ and R¹⁶, the same or different, represent hydrogen or lower alkyl)].

The present invention also provides a thiadiazole derivative represented by the formula [II] ##STR6## [wherein Y represents oxygen or sulfur, R¹⁷ and R¹⁸, the same or different, liner or branched lower alkyl, cycloalkyl or lower alkoxyalkyl, or R¹⁷ and R¹⁸ cooperatively form ##STR7## (wherein E² represents --CH₂ --, nitrogen or oxygen; n, o, p and q, the same or different, represent an integer of 0-2; R¹⁹, R²⁰, R²¹ and R²², the same or different, represent hydrogen or lower alkyl)].

The present invention further provides a thiadiazole derivative represented by the formula [III] ##STR8## (wherein R²³ represents phenyl which is substituted with C₁ -C₆ linear or branched alkyl, branched C₁ -C₈ alkenyl or cycloalkenyl which may be substituted with C₁ -C₆ linear or branched alkyl).

The present invention still further provides a thiadiazole derivative represented by the formula [IV] ##STR9## [wherein R²⁴ and R²⁵, the same or different, represent hydrogen or halogen; R²⁶ and R²⁷, the same or different, represent hydrogen, lower alkyl, --COR²⁸ (wherein R²⁸ represents lower alkyl or amino group which may be substituted with lower alkyl), or R²⁶ and R²⁷ cooperatively form phthaloyl group].

The present invention also provides a process for preparing a thiadiazole derivative represented by the formula [V] ##STR10## [wherein R²⁴ and R²⁵ represent the same meaning as in formula [IV]; R²⁸ and R²⁹, the same or different, represent hydrogen or C₁ -C₆ lower alkyl] comprising reacting a thiadiazole derivative represented by the formula [VI] ##STR11## (wherein R²⁴ and R²⁵ represent the same meaning as in formula [IV]) with an amine represented by the formula [VII]

    NHR.sup.28 R.sup.29

(wherein R²⁸ and R²⁹ represent the same meaning as in formula [V]).

The present invention still further provides a process for preparing a thiadiazole derivative represented by the formula [VIII] ##STR12## (wherein R²⁴ and R²⁵ represent the same meaning as in formula [IV]) comprising reacting the thiadiazole derivative represented by above-described formula [VI] with potassium phthalimide.

The present invention still further provides a process for preparing a thiadiazole derivative represented by the formula [IX] ##STR13## (wherein R²⁴ and R²⁵ represent the same meaning as in formula [IV]) comprising hydrolyzing said thiadiazole derivative represented by the above-described formula [VIII].

The present invention also provides herbicide compositions comprising a herbicidally effective amount of one of said thiadiazole derivatives of the present invention in an agriculturally acceptable carrier.

By the present invention, novel compounds with excellent herbicidal activities and wide herbicidal spectrum and process for preparing the same, as well as herbicide compositions containing the same as an effective ingredient were provided. The herbicide compositions of the present invention can inhibit the growth of various weeds from before the germination to the growth phase thereof. The herbicide compositions of the present invention have high safety, that is, they do not substantially damage useful crops. Thus, the herbicide composition of the present invention may effectively be used for inhibiting the growth of weeds in paddy fields and in the fields of various crops, vegetables, fruits and mulberry, as well as for inhibiting the growth of weeds in the ground other than field. The herbicide compositions of the present invention are especially effective for inhibiting the growth of weeds in paddy fields.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As mentioned above, according to a first aspect of the present invention, the thiadiazole derivatives represented by the formula [I] are provided. It should be noted that the term "lower" means C₁ -C₆ in this specification and claims unless otherwise specified.

The thiadiazole derivatives represented by the formula [I] may be prepared by reacting a corresponding amino acid amide or a hydrogen halide salt thereof represented by the formula [X] with sulfur monochloride or thionyl chloride according to the method described in Journal of Organic Chemistry, p. 2823 (1967). ##STR14## (wherein X, V and Z represent the same meaning as in formula [I], and Q represents halogen).

This reaction may usually be carried out in a solvent at 20°-100° C. for 1-24 hours.

Preferred examples of the solvent which may be used in this reaction may include aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran; halogenated hydrocarbons such as chloroform; and polar solvents such as nitromethane, acetonitrile and N,N-dimethylformamide.

The ratio of the reactants may usually be one equivalent of the amino acid amide to 3-4 equivalents of the sulfur monochloride or thionyl chloride.

The thiadiazole derivatives of the formula [I] may also be prepared by reacting a thiadiazole derivative represented by the formula [XI] with A--Q (wherein A represents the same meaning as in formula [I] and Q' represents halogen), R⁹ OC(═O)R⁹ (wherein R⁹ represents the same meaning as in formula [I], or with R¹⁰ C(═O)OC(═O)R¹⁰ (wherein R¹⁰ represents the same meaning as in formula [II]). ##STR15## (wherein X, Y, Z and V represent the same meaning as in formula [I]).

This reaction may usually be carried out in a solvent and in the presence of a base at 0°-150° C. for several minutes to 48 hours.

Preferred examples of the solvent which may be used in this reaction may include ketones such as acetone and methylethyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane and chlorobenzene; tertially amines such as pyridine, triethylamine and N,N-dimethylaniline; polar solvents such as acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphoric triamide.

Preferred examples of the base which may be used in the reaction may include, organic bases such as pyridine, triethylamine and N,N-dimethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; and alkaline metal alkoxides such as sodium methoxide and sodium ethoxide.

Usually, 1-2 equivalents of A--Q, R⁹ OC(═O)OR⁹ or R¹⁰ C(═O)OC(═O)R¹⁰ and 1-5 equivalents of bases are used for one equivalent of the thiadiazole derivative.

The thiadiazole derivatives represented by the formula [I] wherein A represents --COOR⁹ or CWNR¹¹ R¹² may be prepared as follows: That is, the thiadiazole derivative of the formula [XI] is reacted with phosgene, thiophosgene, trichloromethyl chloroformate or bis(trichloromethyl) carbonate in the presence or absence of a solvent in the presence or absence of a base at 0°-100° C. for several minutes to 48 hours.

Preferred examples of the solvent which may be used in this reaction may include aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride.

Preferred examples of the base which may be used in this reaction may include organic bases such as pyridine, triethylamine and N,N-dimethylaniline; and inorganic bases such as sodium hydrogen carbonate and sodium carbonate.

Then the resultant is reacted with a corresponding alcohol or amine in the presence or absence of a solvent and in the presence or absence of a base at 0°-150° C. for several minutes to 48 hours, thereby the desired thiadiazole derivative may be obtained.

Preferred examples of the solvent which may be used in this reaction may include ketones such as acetone and methylethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane and carbon tetrachloride; tertiary amines such as pyridine, triethylamine and N,N-dimethylaniline; polar solvents such as acetonitrile, N,N-dimethylformamide, acetonitrile, dimethylsulfoxide and 1,3-dimethyl-2-imidazolidinone.

Preferred examples of the base which may be used in this reaction may include organic bases such as pyridine and triethylamine; and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydrogen carbonate.

The thiadiazole derivatives represented by the formula [I] wherein A represents --CWNR¹¹ R¹² may be prepared by reacting the thiadiazole derivative of the above-described formula [XI] with a corresponding isocyanate in the presence or absence of a solvent in the presence or absence of a base at 0°-150° C. for several minutes to 48 hours.

Preferred examples of the solvent which may be used in this reaction may include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; and polar solvents such as pyridine, triethylamine, N,N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphoric triamide.

Preferred examples of the base which may be used in this reaction may include organic bases such as pyridine, triethylamine and N,N-dimethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride.

The thiadiazole derivatives represented by the formula [I] wherein Y represents sulfur and A represents hydrogen may be prepared by thermally converting a corresponding thionocarbamate to the corresponding thiolcarbamate and by subsequent hydrolysis.

This reaction may be carried out under nitrogen atmosphere in the absence of a solvent at 130°-200° C. for several minutes to 24 hours, followed by the hydrolysis.

Further, in cases where at least one of X, V and Z in formula [I] is nitro, the thiadiazole derivative of the formula [I] may be prepared by reacting the thiadiazole derivative represented by the formula [XII] with conc. sulfuric acid/conc. nitric acid at -10° C. to 100° C. for several minutes to 24 hours. ##STR16## (wherein X and V represent the same meaning as in formula [I]) Usually, 4 parts by weight of the thiadiazole derivative of the formula [XII] may be reacted with 10-100 parts by weight of conc. sulfuric acid and 1-100 parts by weight of conc. nitric acid.

In a second aspect of the present invention, thiadiazole derivatives represented by the above-described formula [II3 are provided.

Among the groups designated by R¹⁷ and R¹⁸ in the formula [II], those preferred are C₁ -C₆ linear or branched lower alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl; C₁ -C₇ cycloalkyl groups such as cyclopentyl, cyclohexyl and cyloheptyl; and alkoxyalkyl groups in which an alkyl group is substituted with C₁ -C₆ linear or branched lower alkoxy group such as methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl and isopropoxypropyl. R¹⁷ and R¹⁸ may also cooperatively form a cyclic amine. Preferred examples of the cyclic amine may include pyrrolidine, piperidine, hexamethyleneamine, morpholine and piperazine which may be substituted with C₁ -C₄ linear or branched lower alkyl.

R¹⁷ and R¹⁸ in the formula [II] most preferably represent lower alkyl, cycloalkyl or alkyleneamine.

The thiadiazole derivatives represented by the formula [II] may be prepared by reacting a corresponding amine, carbonyl sulfide and 3-chloromethyl-1,2,5-thiadiazole in a solvent in the presence or absence of a base according to the method described below (Japanese Laid Open Patent Application (Kokai) No. 73732/79).

The dithiol carbamates may also be prepared in the similar manner by reacting a corresponding amine, carbon disulfide and 3-chloromethyl-1,2,5-thiadiazole in a solvent in the presence or absence of a base.

These reactions may be carried out by reacting the above-described reactants in a solvent at 0°-100° C. for 1-24 hours.

Preferred examples of the solvent which may be employed in these reactions may include water; alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; and pyridine. Among these, most preferred are water, ethanol, toluene and pyridine.

Preferred examples of the base which may be employed in these reactions may include organic bases such as pyridine, triethylamine and N,N-dimethylaniline, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride. Among these, most preferred is sodium hydroxide.

The amount of the amine subjected to the reaction may be not less than 2 equivalents with respect to 1 equivalent of 3-chloromethyl-1,2,5-thiadiazole in the absence of the base, or not less than 1 equivalent with respect to 1 equivalent of 3-chloromethyl-1,2,5-thiadiazole in the presence of the base.

The amount of the base may be not less than 1 equivalent with respect to 1 equivalent of 3-chloromethyl-1,2,5-thiadiazole.

In a third aspect of the present invention, the thiadiazole derivatives represented by the above-described formula [III] are provided.

In the formula [III], R²³ represents phenyl group which is substituted with C₁ -C₆ alkyl such as 2,6-dimethylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, 2,6-dipropylphenyl, 2-methyl-6-propylphenyl and 2,4,6-trimethylphenyl; C₁ -C₈ alkenyl such as 1-propenyl, 1-methyl-1-propenyl and 1,3-dimethylbutenyl; or cycloalkenyl which may be substituted with C₁ -C₆ linear or branched alkyl such as 1-cyclohexyl, 1-cyclopentyl, 2,6-dimethyl-1-cyclohexynyl and 2,6-dimethyl-1-cyclopentenyl.

The thiadiazole derivative of the formula [III] may be prepared according to one of the following reactions [A] to [C]. ##STR17## (wherein Ar represents phenyl group which is substituted with C₁ -C₆ linear or branched alkyl) ##STR18## (wherein Ar represents the same meaning as in formula [XIII]) ##STR19## (wherein R³⁰ and R³¹, the same or different, represent C₁ - C₆ linear or branched alkyl or R³⁰ and R³¹ cooperatively form C₁ -C₁₈ alicyclic group).

In the Reaction [A], the amine represented by the formula [XIII] and chloroacetyl chloride represented by the formula [XIV] are reacted in the presence or absence of a solvent in the presence of a base at 0°-150° C. for several minutes to 48 hours.

The reaction may preferably be carried out in the presence of a solvent. Preferred examples of the solvent which may be employed in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and diethyleneglycoldimethyl ether; ketones such as acetone, methylethyl ketone, methylisobutyl ketone and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and isobutylonitrile; dimethylforamide; and dimethylsulfoxide.

Preferred examples of the base which may be used in Reaction [A] may include organic bases such as pyridine, triethylamine and N,N-diethylaniline; alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkaline metal carbonates such as sodium carbonate and potassium carbonate.

In Reaction [A], 1-10 equivalents of the compound of the formula [XIV] and 1-10 equivalents of the base may usually be used per one equivalent of the compound of the formula [XIII].

The reaction [B] may be carried out by reacting the amide represented by the formula [XV] with 3-chloromethyl-1,2,5-thiadiazole of the formula [XVI] in a solvent in the presence of a base at 0°-150° C. for several minutes to 48 hours.

The reaction may preferably be carried out in a solvent. Preferred examples of the solvent may include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, diethyleneglycol dimethylether; ketones such as acetone, methylethyl ketone, methylisobutyl ketone and cyclohexanone; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and isobutylonitrile; dimethylformamide; and dimethylsulfoxide.

Preferred examples of the base which may be used in Reaction [B] are the same as those preferred in Reaction [A].

In Reaction [B], 1-10 equivalents of the compound of the formula [XVI] and 1-10 equivalents of the base may usually be used per one equivalent of the compound the formula [XV].

The Reaction [C] may be carried out by reacting the amine of the formula [XVII] with chloroacetyl chloride of the formula [XIV] in the presence or absence of a solvent in the presence or absence of a base at 0°-150° C. for several minutes to 48 hours.

The Reaction [C] may preferably be carried out in a solvent in the absence of a base.

Preferred examples of the solvent which may be employed in Reaction [C] may include those preferred in Reaction [B].

Examples of the base which may be employed in Reaction [C] may include those preferred in Reaction [A].

In Reaction [C], 1-10 equivalents of the compound of the formula [XIV] and 1-10 equivalents of the base may usually be used per one equivalent of the compound of the formula [XVII].

In a fourth aspect of the present invention, a thiadiazole derivative of the above-described formula [IV] is provided.

In the formula [IV], R²⁴ and R²⁵, the same or different, represents hydrogen or halogen such as fluorine, chlorine, bromine and iodine; R²⁶ and R²⁷, the same or different, represents hydrogen, lower alkyl preferably C₁ -C₆ linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and isohexyl, or --COR²⁸ (wherein R²⁸ represents lower alkyl or amino group which may be substituted with lower alkyl), or R²⁶ and R²⁷ cooperatively form phthaloyl group.

Among the compounds represented by the formula [IV], those represented by the above-described formula [V] may be prepared by reacting the thiadiazole derivative of the above-described formula [VI] with the amine of the above-described formula [VII]. This reaction may be carried out in a solvent in the presence or absence of copper and/or cuprous chloride at 60°-150° C. for several minutes to 48 hours. In the formula [VII], preferred examples of the lower alkyl groups represented by R²⁸ and R²⁹ may be C₁ -C₆ linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and isohexyl.

Preferred examples of the solvent which may be employed in this reaction may include alcohols such as methanol and ethanol; polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphoric triamide; and water.

In this reaction, 1-100 equivalents of the amine of the formula [VIII], 1-10 equivalents of copper and 1-10 equivalents of cuprous chloride may be used per 1 equivalent of the thiadiazole derivative of the formula [XIII].

Among the thiadiazole derivatives represented by the formula [IV], those represented by the above-described formula [VIII] may be prepared by reacting the thiadiazole derivative of the above-described formula [VI] with potassium phthalimide. This reaction may be carried out in a solvent at 80°-150° C. for several minutes to 48 hours.

Preferred examples of the solvent which may be used in this reaction may include alcohols such as methanol and ethanol; polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphoric triamide; and water.

In this reaction, 1-10 equivalents of potassium phthalimide may be used per one equivalent of the thiadiazole derivative of the formula [VI].

Among the thiadiazole derivatives represented by the formula [IV], those represented by the above-described formula [IX] may be prepared by hydrolyzing the thiadiazole derivative of the above-described formula [VIII]. This hydrolysis may be carried out by treating the thiadiazole derivative of the formula [VIII] with an acid such as hydrochloric acid and sulfuric acid or hydrazine in a solvent at 50°-100° C. for several minutes to 24 hours.

Preferred examples of the solvent which may be used in this reaction may include alcohols such as methanol and ethanol; and water.

In this reaction, 1-100 equivalents of the acid or hydrazine is used for one equivalent of the thiadiazole derivative of the formula [VIII].

Among the thiadiazole derivatives of the formula [IV], those wherein R²⁶ and R²⁷ represent --COR²⁸ may be prepared by reacting the thiadiazole derivative of the above-described formula [IX] with X'--COR²⁸ (wherein X' represents halogen and R²⁸ represents the same meaning as in formula [IV]). This reaction may be carried out in the presence of a base and a solvent at 40°-150° C. for several minutes to 24 hours.

Preferred examples of the solvent which may be employed in this reaction may include ketones such as acetone and methylethyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane and chlorobenzene; tertiary amines such as pyridine, triethylamine and N,N-dimethylaniline; and polar solvents such as acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphoric triamide.

Preferred examples of the base which may be employed in this reaction may include organic bases such as pyridine, triethylamine and N,N-dimethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride; and alkaline earth metal alkoxide such as sodium methoxide and sodium ethoxide.

In this reaction, 1-5 equivalents of X'--COR²⁸ and 1-10 equivalents of the base are used for one equivalent of thiadiazole derivative of the formula [IX].

In still another aspect of the present invention, a herbicide composition comprising the thiadiazole derivative of the present invention represented by the formula [I], [II], [III] or [IV] in an agriculturally acceptable carrier is provided.

The herbicide composition of the present invention has excellent herbicidal effectiveness while it does not substantially damage the useful crops. More particularly, the herbicide composition of the present invention can inhibit the growth of weeds in fields such as slender rush, purslane, cocklebur, coreopsis species, ragweed, common lambsquarters, pale smartweed, chickweed, shepherd's purse, chickweed, jimsonweed, morningglory, nightshade, honblt, plaintain, velvetleaf, woodsorrel, catchweed badstraw, buckwheat, fleabane, horseweed, daisy fleabane, barnyardgrass, green foxtail, large crabgrass, annual bluegrass, water foxtail, oats and johnsongrass, as well as the weeds in paddy fields such as barnyardgrass, falsepinpernel, spindle-flowered rotala, small flower umbrellaplant, bulrush, slender spikerush, water mutgrass, monochoria and arrowhead species. The herbicidal effect is exhibited either before the germination of the weeds or during the growth of the weeds. On the other hand, the herbicide composition of the present invention does not substantially damage the useful crops such as corn, wheat, rice, soybean, cotton and beat.

The herbicide composition of the present invention may contain other agricultural chemicals such as pesticides,fungicides, herbicides and plant growth regulators, as well as fertilizers and soil improvers. In particular, by blending one or more herbicides, the labor of application of the herbicides is reduced and the range of the weeds which can be controlled by the composition may be widen. Examples of such herbicides may include triazine-based herbicides such as 2,4-bis(ethylamino)-6-ethylthio-1,3,5-triazine (common name: simetryne), 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine (common name: prometryne) and 2-(1,2-dimethylpropylamino)-4-ethylamino-6-methylthio-1,3,5-triazine (common name: dimethametryn); carbamate-based herbicides such as S-4-chlorobenzyl N,N-diethylthiocarbamate (common name: benthiocarb), S-α,α-dimethylbenzyl N,N-pentamethylenethio carbamate (common name: dimepiperate), S-benzyl N-ethyl-N-(1,2-dimethylpropyl)thiocarbamate (common name: esprocarb), S-ethylhexahydro-1H-azepine-1-carbothioate (common name: molinate), and O-3-tert-butylphenyl N-(6-methoxy-2-pyridyl)-N-methylthiocarbamate (common name: piributycarb); phenoxy-based herbicides such as 2,4-D, MCPB, 2-(2-naphthyloxy)propionanilide (common name: naproanilide), and 2-(2,4-dichloro-3-methylphenoxy)propionanilide (common name: clomeprop); diphenyl ether-based herbicides such as 2,4,6-trichlorophenyl 4-nitrophenyl ether (common name: chloronitrofen), 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether (common name: chloromethoxynil), 2,4-dichlorophenyl 3-methoxycarbonyl-4-nitrophenyl ether (common name: bifenox) and 2-chloro-4-trifluoromethylphenyl 4-nitro-3-(tetrahydropyrane-3-yloxy)phenyl ether (test code: MT-124); amide-based herbicides such as N-butoxymethyl-2-chloro-2',6'-diethylacetoanilide (common name: butachlor), N-propoxyethyl-2-chloro2',6'-diethylacetoanilide (common name: pretilachlor), N-methyl-2-(2-benzothiazolyloxy)acetoanilide (common name: mefenacet), 2',3'-dichloro-4-ethoxymathoxybenzanilide (test code: HW-52), N-(α,α-dimethylbenzyl)-2-bromo-3,3-dimethylbutylamide (common name: bromobutide), and 3',4'-dichloropropionanilide (common name: propanil); urea-based herbicides such as 1-(α,α-dimethylbenzyl)-3-(4-methylphenyl)urea (common name: dymron) and 1-(2-chlorobenzyl)-3-(α,α-dimethylbenzyl)urea (test code: JC-940); quinone-based herbicides such as 2-amino-3-chloro-1,4-naphthoquinone (common name: ACN); heterocycle-based herbicides such as 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl p-toluenesulfonate (common name: pyrazolate), 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-phenasyloxypirazole (common name: pyrazoxyfen), 4-(2,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-(4-methylphenasyloxy)pyrazole (common name: benzofenap), 5-benzyloxy-4-(2,4-dichlorobenzoyl)-1-methylpirazole (test name: NC-310), 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazole-2-(3H)-one (common name: oxadiazone), 3,7-dichloro-8-quinoline carboxylic acid (common name: quinolorac), 3-chloro-2-[2-fluoro-4-chloro-5-(1-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-imidazole (test code: S-275), 3-isopropyl-2,1,3-benzothiaziadinone-4)-2,2-dioxide (common name: bentazone), and 1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide (test code: KNW-242); organic phosphur-based herbicides such as O,O-diisopropyl-2-(benzenesulfonamide)ethylenedithiophosphate (common code: SAP); and sulfonylurea-based herbicides such as methyl 2-[[[[[(4,6 -dimethoxypyrimidine-2-yl)amino]carbonyl]amino]sulfonyl]methyl]benzoate (common name: londax) and ethyl 5-[3-(4,6-dimethoxypyrimidine-2-yl)ureidosulfonyl]-1-methylpirazole-4-carboxylate (common name: pyrazosulfuron ethyl).

The herbicide composition of the present invention may be in the form of an emulsifiable concentrate, wettable powder, flowable powder, granules or powder. These formulations may be prepared by formulating the effective ingredient of the present invention with an agriculturally acceptable carrier such as a solid carrier, solvent, surfactant and a formulation aid.

Examples of the solid carrier include kaolin, clay, bentonite, diatomaceous earth, acidic terra abla, white carbon and pumice powder. Examples of the solvent include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethyleneglycol and cellosolve; ketones such as acetone and cyclohexanone; mineral oil; dimethylsulfoxide; N,N-dimethylformamide; acetonitrile and water. Examples of the surfactants include anion surfactants such as salts of alkyl sulfate, alkyl sulfonate and aryl sulfonate; and non-ion surfactants such as polyoxyethyleneglycol ethers, polyoxyethyleneglycol esters and polyol esters. Examples of other formulation aids include polyvinyl alcohol, lignin sulfonate and acacia.

The herbicide composition of the present invention usually contains 0.1-90% by weight, preferably 1-80% by weight of the effective ingredient of the present invention.

The amount of the compound of the present invention to be applied to the field varies depending on the weather conditions, formulation of the composition, timing of application, method of application, field conditions, species and stage of growth of the weeds and on the crops. Usually, the amount to be applied may be 1-1000 g/10 a, preferably 2-500 g/10 a in terms of the weight of the effective ingredient of the present invention.

The herbicide composition of the present invention may directly be applied to the leaves or stems of weeds or to the field before the germination of the weeds.

The invention will now be described by way of examples thereof. The examples are presented for the illustration purpose only and should not be interpreted in any restrictive way.

EXAMPLE 1 Preparation of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole (Compound No. 11 (see Table 1))

In N,N-dimethylformamide, 14.5 g of 2,6-dichlorophenyl glycine amide hydrobromic acid salt was dissolved and 19.5 g of sulfur monochloride was added thereto. The mixture was stirred for 12 hours at room temperature. The mixture was then poured into water and was converted to alkaline with sodium hydroxide, followed by removal of insoluble materials by filtration. The filtrate was converted to acidic with hydrochloric acid and the generated precipitates were extracted with ether. The ether layer was washed twice with dilute hydrochloric acid and then twice with saturated sodium chloride solution, followed by drying over anhydrous sodium sulfate. The solvent was evaporated off and the obtained crystals were recrystallized from chloroform to obtain 9.5 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole.

m.p.: 194°-195° C.

¹ H-NMR (CDCl₃, δ ppm) 7.3-7.6 (m).

IR (KBr, cm⁻¹) 3200-2400, 1540, 1505, 1435, 1230, 880, 790, 775.

Elemental analysis for C₈ H₄ N₂ OSCl₂ ; Calcd.: C;38.88, H;1.63, N;11.33; Found: C;39.00, H;1.48, N;11.53.

EXAMPLE 2 Preparation of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethyl carbamate (Compound No. 7)

In acetonitrile, 0.25 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole and 0.15 g of potassium carbonate were suspended and 0.12 g of dimethylcarbamoyl chloride was added thereto. The mixture was heated to reflux for 12 hours. After allowing to cool, the mixture was poured into water and extracted with ether. The ether layer was washed twice with dilute sodium hydroxide solution, twice with water and twice with aqueous saturated sodium chloride solution. The extract was dried over anhydrous sodium sulfate and the resultant was condensed, followed by silica gel column chromatography to obtain 0.25 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethyl carbamate.

m.p.: 115°-116° C.

¹ H-NMR (CDCl₃, δppm) 2.87 (s, 3H), 2.93 (s, 3H), 7.2-7.45 (m, 3H).

IR (KBr, cm⁻¹) 1735, 1365, 1235, 1150, 785.

Elemental analysis for C₁₁ H₉ N₃ OSCl₂ ; Calcd.: C;41.52, H;2.85, N;13.20; Found: C;41.58, H;2.86, N;13.04.

EXAMPLE 3 Preparation of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl acetate (Compound No. 66)

In ether, 0.5 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole and 0.18 g of pyridine were dissolved and 0.23 g of acetic anhydride was added thereto. The mixture was stirred for 3 hours at room temperature. The reaction mixture was poured into water and extracted with ether. The ether layer was washed twice with aqueous dilute sodium hydroxide solution, twice with water and twice with aqueous saturated sodium chloride solution. The resultant was dried over anhydrous sodium sulfate and concentrated, followed by silica gel column chromatography to obtain 0.41 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl acetate.

m.p.:.56°-59° C.

¹ H-NMR (CDCl₃, δppm) 2.17 (s, 3H), 7.15-7.4 (m, 3H)

IR (KBr, cm⁻¹) 1795, 1430, 1175, 780.

Elemental analysis for C₁₀ H₆ N₂ O₂ SCl₂ ; Calcd.: C;41.54, H;2.09, N;9.68; Found: C;41.23, H;2.27, N;9.84.

EXAMPLE 4 Preparation of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N-(3-methoxypropyl)-N-methyl carbamate (Compound No. 62)

In benzene, 0.49 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole and 0.21 g of bis(trichloromethyl)carbonate were dissolved. To the mixture, 0.2 g of pyridine was added and the mixture was stirred at room temperature for 12 hours. Then 0.41 g of N-methyl-N-(3-methoxypropyl)amine was added to the mixture and the resulting mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into water and was extracted with ether. The ether layer was washed three times with dilute aqueous sodium hydroxide solution, three times with dilute hydrochloric acid, twice with water and then twice with aqueous saturated sodium chloride solution. The resultant was dried over anhydrous sodium sulfate and condensed, followed by silica gel column chromatography to obtain 0.38 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N-(3-methoxypropyl)-N-methyl carbamate.

n_(D) ²⁵.0 : 1.5638

¹ H-NMR (CDCl₃, δppm): 1.4-2.0 (m, 2H), 2.92 (broad s, 3H), 3.1-3.6 (m, 7H), 7.25-7.5 (m, 3H).

IR (NaCl, cm⁻¹) 1745, 1430, 1385, 1230, 1120, 790.

Elemental analysis for C₁₄ H₁₅ N₃ O₃ SCl₂ ; Calcd.: C;44.69, H;4.01, N;11.16; Found: C;44.34, H;4.05, N;10.92.

EXAMPLE 5 Preparation of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethylthiol carbamate (Compound No. 35)

Under nitrogen atmosphere, 1.34 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethylthiono carbamate was heated to 180° C. After allowing to cool, the reaction mixture was purified by silica gel column chromatography to obtain 0.8 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethylthiol carbamate

m.p.: 168°-170° C.

¹ H-NMR (CDCl₃, δppm) 2.93 (s, 6H), 7.2-7.45 (m, 3H).

IR (KBr, cm⁻¹) 1690, 1430, 1090, 785.

Elemental analysis for C₁₁ H₉ N₃ OS₂ Cl₂ ; Calcd.: C;39.52, H;2.71, N;12.57; Found: C;39.38, H;2.83, N;12.79.

EXAMPLE 6 Preparation of 3-(2,6-dichlorophenyl)-4-mercapto-1,2,5-thiadiazole (Compound No. 38)

To a mixed solvent of 15 ml of ethanol and 0.3 ml of water, 0.6 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N,N-dimethylthiol carbamate and 0.28 g of potassium hydroxide were added and the mixture was heated to reflux for 15 hours. Ethanol was removed from the reaction mixture and aqueous dilute sodium hydroxide solution was added to the resulting mixture, followed by extraction with ether. The aqueous layer was extracted with ether after converting it to acidic with hydrochloric acid. The ether layers were washed twice with dilute hydrochloric acid and twice with saturated aqueous sodium chloride solution, and the resultant was dried over anhydrous sodium sulfate, followed by removal of the solvent to obtain 0.4 g of 3-(2,6-dichlorophenyl)-4-mercapto-1,2,5-thiadiazole.

m.p.: 91°-94° C.

¹ H-NMR (CDCl₃, δppm) 3.09 (broad s, 1H), 7.53 (s, 3H).

IR (KBr, cm⁻¹) 2550, 1430, 1345, 1175, 820, 790, 785.

Elemental analysis for C₈ H₄ N₂ S₂ Cl₂ ; Calcd.: C;36.51, H;1.53, N;10.64; Found: C;36.82, H;1.38, N;10.58.

EXAMPLE 7 Preparation of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N-methyl carbamate (Compound No. 75)

In pyridine, 0.25 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole was dissolved and 0.17 g of methyl isocyanate was added to the solution. The mixture was stirred at room temperature for 19 hours. The reaction mixture was then poured into water and extracted with ether. The ether layer was washed twice with dilute hydrochloric acid and twice with saturated aqueous sodium chloride solution, and the resultant was dried over anhydrous sodium sulfate. The resultant was condensed and purified by silica gel chromatography to obtain 0.24 g of 4-(2,6-dichlorophenyl)-1,2,5-thiadiazol-3-yl N-methyl carbamate.

m.p.: 118°-122° C.

¹ H-NMR (CDCl₃, δppm) 2.75 (d, J=5Hz, 3H), 5.3 (broad s, 1H), 7.2-7.5 (m 3H).

IR (KBr, cm⁻¹) 3290, 1760, 1730, 1400, 1225.

Elemental analysis for C₁₀ H₇ N₃ O₂ SCl₂ ; Calcd.: C;39.49, H;2.31, N;13.81; Found: C;39.66, H;2.48, N;14.13.

In the similar manner, various compounds represented by the formula [I] were prepared. The structures thereof as well as the physical properties are shown in Table 1.

EXAMPLE 8 Preparation of 4-(2,6-dichloro-3-nitrophenyl)-3-yl methyl carbonate (Compound No. 104)

To mixed acid (mixture of 9 ml of concentrated sulfuric acid and 9 ml of concentrated nitric acid), 2.75 g of 3-(2,6-dichlorophenyl)-4-hydroxy-1,2,5-thiadiazole was added and the resulting mixture was stirred for 4 hours at room temperature. The resulting reactin mixture was poured into water and the resultant was extracted with ether. The ether layer was washed twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 3.15 g of 4-(2,6-dichloro-3-nitrophenyl)-3-yl methyl carbonate.

Viscose Oil

¹ H-NMR (solvent: CDCl₃, δppm) 3.93 (s,3H), 7.62(d,J=8.5Hz,1H), 7.59(d,J=8.5Hz, 1H).

IR (NaCl, cm⁻): 1785, 1540, 1530, 1250, 1220.

Elementary Analysis (%): Calcd.: C; 34.30, H;1.43, N;12.00; Found: C;34.30, H:1.56, N;11.97.

In the similar manner, various compounds represented by the formula [I] were prepared. The structures thereof as well as the physical properties are shown in Table.

EXAMPLE 9 Preparation of Wettable Powder

Ten parts of the compound of the present invention, 86.5 parts by weight of Zeaklite (commercially available from Zeaklite Kagaku Kogyo), 2 parts by weight of New Cargen NV-406 (commercially available from Takemoto Oil) and 1.5 parts by weight of Disksol WA (commercially available from Daiichi Kogyo Seiyaku) were mixed and the mixture was pulverized to obtain wettable powder.

EXAMPLE 10 Preparation of Emulsifiable Concentrate

Five parts by weight of the compound of the present invention, 75 parts by weight of xylene and 20 parts by weight of Solpol 2806B (a surfactant commercially available from Toho Kagaku Kogyo) were mixed and the mixture was uniformly stirred to obtain emulsifiable concentrate.

EXAMPLE 11 Preparation of Granules

Ten parts by weight of the compound of the present invention, 50 parts by weight of bentonite, 35 parts by weight of Kunilite (commercially available from Kunimine Kogyo) and 5 parts by weight of Solpol 800A (a surfactant commercially available from Toho Kagaku Kogyo) were mixed and the mixture was pulverized. Water was added to the resulting mixture and the mixture was stirred. The mixture was then formed into granules and dried to obtain granules.

EXAMPLE 12 Test for Evaluation of Effectiveness in Growth Inhibition 10 of Weeds by Treatment of Water in Paddy Field

In a plastic pot of 100 cm², plowed soil of paddy field was packed and the seeds of weeds shown in Table 2 were sown. Two two-leaves stage seedlings of paddy rice were planted per 1 pot and the soil was covered with water of 2 cm thickness. In the germination period of the weeds, the herbicide composition in the form of wettable powder formulated as in Example 9 was dropped on the water in the amount shown in Table 2. The pots were placed in a green house and water was appropriately supplied to the pots. After 20 days from the treatment with the herbicide, the herbicidal effectiveness and damage of the rice were examined. The results are shown in Table 2. The herbicide effectiveness as well as the damage of the crops is classified into 6 ranks according to the following criteria:

    ______________________________________                                         Herbicidal Effectiveness                                                                       Rate of Growth Inhibition                                      ______________________________________                                         0               0-9%                                                           1               10-29%                                                         2               30-49%                                                         3               50-69%                                                         4               70-89%                                                         5                90-100%                                                       ______________________________________                                    

EXAMPLE 13 Preparation of S-3-1,2,5-thiadiazolyl methyl N,N-diethylthiol carbamate (Compound No. 131)

In a 50 ml pear-shaped flask, 1.08 g of diethylamine and 1.08 g of water were placed and 0.89 g of carbonyl sulfide was bubbled at 15°-20° C. with stirring and cooling with water. To the mixture, 1 g of 3-chloromethyl-1.2.5-thiadiazole was added dropwise. After completion of the addition, the mixture was heated at 50° C. for 3 hours under stirring. After allowing to cool, the mixture was extracted with ether. The organic layer was washed with 1N hydrochloric acid and water, and the resultant was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was distilled to obtain 1.05 g of S-3-1,2,5-thiadiazolyl methyl N,N-diethylthiol carbamate (Compound No. 131).

b.p.: 106° C./0.5 mmHg

¹ H-NMR (CDCl₃, δppm) 1.0 (6H, t, d=7Hz), 3.28 (4H, q, J=7Hz), 4.30 (2H,s), 8.5 (1H, s).

IR (NaCl, cm⁻¹) 1650.

Elemental analysis for C₈ H₁₃ N₃ OS₂ ; Calcd.: C;41.53, H;5.66, N;18.16; Found: C;41.10, H;5.46, N;17.99.

EXAMPLE 14 Preparation of S-3-1,2,5-thiadiazolylmethyl N,N-dimethylthiol carbamate (Compound No. 132)

To a solution composed of 1.34 g of dimethylamine and 1.34 g of water, carbonyl sulfide was bubbled to saturation under cooling with water, and 1 g of 3-chloromethyl-1,2,5-thiadiazole was added dropwise thereto. Thereafter, the procedure in Example 13 was followed to obtain 0.73 g of S-3-1,2,5-thiadiazolylmethyl N,N-dimethylthiol carbamate (Compound No. 132).

b.p.: 99° C./0.4 mmHg

¹ H-NMR (CCl₄, δppm) 2.95 (6H, s), 4.32 (2H, s), 8.5(1H, s).

IR (NaCl, cm⁻¹) 1650.

Elemental analysis for C₆ H₉ N₃ OS₂ ; Calcd.: C;35.45, H;4.46, N;20.78; Found: C;35.78, H;4.47, N;20.78.

EXAMPLE 15 Preparation of S-3-1,2,5-thiadiazolylmethyl N,N-diisopropylthiol carbamate (Compound No. 133)

To a solution composed of 1.50 g of diisopropylamine and 1.5 g of water, carbonyl sulfide was bubbled to saturation and then 1 g of 3-chloromethyl-1,2,5-thiadiazole was dropped into the mixture. The mixture was heated at 50° C. for 3 hours under stirring. After allowing to cool, the mixture was extracted with ether. The organic layer was washed with 1N hydrochloric acid and water, and the resultant was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluant: benzene/ethyl acetate=10/1) to obtain 1.09 g of S-3-1,2,5-thiadiazolylmethyl N,N-diisopropylthiol carbamate (Compound No. 133).

Refractive Index: n_(D) ²⁵ =1.5470

¹ H-NMR (CCl₄, δppm) 1.32 (6H, d, J=7Hz), 3.4-4.2 (2H, m), 4.38 (2H, s), 8.50 (1H, s).

IR (NaCl, cm⁻¹) 1635.

Elemental analysis for C₁₀ H₁₇ N₃ OS₂ ; Calcd.: C;46.30, H;6.60, N;16.19; Found: C;46.40, H;6.69, N;16.29.

EXAMPLE 16 Preparation of S-3-1,2,5-thiadiazolyl N,N-dimethyldithio carbamate (Compound No. 136)

To 1 ml of aqueous solution containing 0.67 g of dimethylamine, 0.57 g of carbon disulfide was added dropwise under cooling in ice. After stirring in ice for 30 minutes, 1 g of 3-chloromethyl-1,2,5-thiadiazole was added to the mixture. Thereafter, the procedure in Example 15 was followed to obtain 1.28 g of S-3-1,2,5-thiadiazolyl N,N-dimethyldithio carbamate (Compound No. 136).

Refractive Index: n_(D) ²⁵ =1.6508.

¹ H-NMR (CCl₄, δppm) 3.40 (6H, s), 4.75 (2H, s), 8.52 (1H, s).

Elemental analysis for C₆ H₉ N₃ OS₂ ; Calcd.: C;32.85, H;4.13, N;19.15; Found: C;32.48, H;4.04, N;19.03.

In the similar manner, various compounds represented by the formula [II] were prepared. The structures thereof as well as the physical properties are shown in Table 3.

EXAMPLE 17 Test for Evaluation of Effectiveness in Growth Inhibition of Weeds by Treatment of Water in Paddy Field

The compounds shown in Table 4 formulated into wettable powder according to Example 9 were tested for their effectiveness in growth inhibition of weeds in the same manner as in Example 12. The results are shown in Table 4.

EXAMPLE 18 Preparation of N-(1,2,5-thiadiazolyl-3-methyl)-N-(2,6-diethylphenyl)-α-chloroacetamide (Compound No. 178)

To a 100 ml three-necked flask, 30 ml of anhydrous dimethylsulfoxide, 0.7 g of pulverized potassium hydroxide powder and 2 g of N-2,6-diethylphenyl-α-chloroacetamide were placed. Under nitrogen atmosphere, the mixture was stirred at room temperature until the mixture became a uniform solution. To the thus obtained uniform solution, 1.2 g of 3-chloromethyl-1,2,5-thiadiazole was added under cooling in ice. After the addition, the mixture was stirred at room temperature for one hour and 30 ml of iced water was added to the reaction mixture. The resulting mixture was then extracted with ether and the organic layer was dried over anhydrous magnesium sulfate, followed by evaporation of the solvent. The residue was purified by silica gel column chromatography to obtain 0.55 g of the desired product.

m.p.: 77.5°-78° C.

IR (KBr, cm⁻¹) 1650.

¹ H-NMR (CDCl₃, δppm) 1.08 (6H, d, J=7Hz), 2.22 (4H, q, J=7Hz), 3.68 (2H, s), 5.00 (2H, s), 6.95-7.32 (3H, m), 8.77 (1H, s).

EXAMPLE 19 Preparation of N-(1,2,5-thiadiazolyl-3-methyl)-N-(2,6-dimethylphenyl)-α-chloroacetamide (Compound No. 179)

The same procedure as in Example 18 was repeated except that 30 ml of dimethylsulfoxide, 0.5 g of potassium hydroxide and 1.58 g of N-(2,6-dimethylphenyl)-α-chloroacetamide were used to obtain 0.9 g of the desired product.

m.p.: 75°-76° C.

IR (KBr, cm⁻¹) 1650.

¹ H-NMR (CDCl₃, δppm) 1.65 (6H, s), 3.70 (2H, s), 5.02 (2H, s), 7.0-7.3 (3H, m), 8.76 (1H, s).

EXAMPLE 20 Preparation of N-(1,2,5-thiadiazolyl-3-methyl)-N-(2-methyl-6-ethylphenyl)-α-chloroacetamide (Compound No. 180)

The same procedure as in Example 18 was repeated except that 10 ml of dimethylsulfoxide, 20 ml of tetrahydrofuran, 0.5 g of potassium hydroxide and 1.47 g of N-2,6-diethylphenyl-α-chloroacetamide were used to obtain 0.49 g of the desired product.

m.p.: 66°-67° C.

IR (KBr, cm⁻¹) 1650.

¹ H-NMR (CDCl₃, δppm) 1.05 (3H, t, J=7Hz), 1.92 (3H, s), 2.27 (2H, q, J=7Hz), 3.80 (2H, s), 5.00 (2H, s), 6.82-7.44 (3H, m), 8.72 (2H, s).

EXAMPLE 21 Preparation of N-(1,2,5-thiadiazolyl-3-methyl)-N-(2,6-dimethyl-1-cyclohexenyl)-α-chloroacetamide (Compound No. 181)

To 10 ml of a solution in toluene containing 0.7 g of 3-(N-2,6-dimethylcyclohexylideneaminomethyl)-1,2,5-thiadiazole obtained by the condensation of 2,6-dimethylcyclohexanone and 3-aminomethyl 1,2,5-thiadiazole, 0.4 g of chloro-α-chloroacetyl was added and the resulting mixture was stirred for 8 hours under heat. After allowing the mixture to cool, the solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography to obtain 0.48 g of the desired product in the form of oil.

Refractive Index: n_(D) ²⁵ =1.5489

IR (NaCl, cm⁻¹) 1665.

¹ H-NMR (CDCl₃, δppm) 0.72-2.75 (13H, m), 3.92 (2H, s), 4.71, 4.87 (2H, s), 8.65 (1H, s).

EXAMPLE 22 Preparation of N-(2-(4-methyl-2-butenyl))-N-(3-(1,2,5-thiadiazolyl)methyl)-α-chloroacetamide (Compound No. 182)

The same procedure as in Example 21 was repeated except that 1 g of a condensate of methylisopropyl ketone and 3-aminomethyl-1,2,5-thiadiazole, and 0.68 g of chloro-α-chloroacetyl was used to obtain 0.9 g of the desired product in the form of oil.

Refractive Index: n_(D) ²⁵ =1.5263.

IR (NaCl, cm⁻¹) 1665.

¹ H-NMR (CDCl₃, δppm) 0.95 (6H, d, J=6.2Hz), 1.89 (3H, s), 2.08-2.82 (1H, m), 4.08 (2H, s), 4.82 (2H, s), 5.11 (1H, s), 8.55 (1H, s).

EXAMPLE 23 Test for Evaluation of Effectiveness in Growth Inhibition of Weeds by Treatment of Water in Paddy Field

The compounds of Compound Nos. 178-182 formulated into wettable powder according to Example 9 were tested for their effectiveness in growth inhibition of weeds in the same manner as in Example 12. The results are shown in Table 5.

EXAMPLE 24 Preparation of 3-amino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole (Compound No. 183)

A solution in methanol containing 5.31 g of 3-chloro-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole, 1.91 g of copper powder and 1.97 g of cuprous chloride saturated with ammonia gas was placed in a stainless steel vessel. After sealing the vessel, the solution was stirred at 120° C. for 24 hours. After allowing the mixture to cool, insoluble materials were removed by filtration. The filtrate was concentrated and the residue was purified by silica gel column chromatography to obtain 2.19 g of 3-amino- 4-(2,6-dichlorophenyl)-1,2,5-thiadiazole.

m.p.: 95°-97° C.

¹ H-NMR (CDCl₃, δppm) 4.52 (s, 2H), 7.2-7.5 (m, 3H).

IR (KBr, cm⁻¹) 3425, 3325, 3210, 1620, 1535, 1490, 1430, 1420, 790, 780.

MS (m/z): 245 (M⁺)

EXAMPLE 25 Preparation of 3-(4-chlorophenyl)-4-phthalimide-1,2,5-thiadiazole

To a solution of 1.16 g of 3-chloro-4-(4-chlorophenyl)-1,2,5-thiadiazole in N,N-dimethylformamide, 1.11 g of potassium phthalimide was added and the mixture was heated to reflux at 110° C. for 12 hours. After allowing to cool, the mixture was poured into water and the resultant was extracted with ether. The ether layer was washed twice with dilute aqueous sodium hydroxide solution, twice with water, and twice with saturated aqueous sodium chloride solution. The resultant was then dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 0.85 g of 3-(4-chlorophenyl)-4-phthalimide-1,2,5-thiadiazole.

m.p.: 152°-153° C.

¹ H-NMR (CDCl₃, δppm) 7.1-7.4 (m, 2H), 7.4-7.7 (m, 2H), 7.7-8.0 (m, 4H).

IR (KBr, cm⁻¹) 1790, 1725, 1440, 1180, 885, 715.

MS (m/z): 341 (M⁺).

EXAMPLE 26 Preparation of 3-amino-4-(4-chlorophenyl)-1,2,5-thiadiazole

To a solution of 0.41 g of 3-(4-chlorophenyl)-4-phthalimide-1,2,5-thiadiazole in ethanol, 0.05 g of 80% aqueous hydrazine solution was added and the mixture was heated to reflux for one hour. After allowing to cool, the mixture was poured into water and extracted with ether. The ether layer was washed twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate and the resultant was concentrated, followed by purification by silica gel column chromatography to obtain 0.21 g of 3-amino-4-(4-chlorophenyl)-1,2,5-thiadiazole.

m.p.: 132°-133° C.

¹ H-NMR (acetone-d₆, δppm) 5.40 (bs, 2H), 7.2-7.5 (m, 2H), 7.5-7.8 (m, 2H).

IR (KBr, cm⁻¹) 3410, 3310, 3190, 1620, 1515, 1495, 1435, 1400, 1090, 830.

MS (m/z): 211 (M⁺).

EXAMPLE 27 Preparation of 3-(2,6-dichlorophenyl)-4-methylamino-1,2,5-thiadiazole (Compound No. 184)

In a stainless steel vessel, 5.31 g of 3-chloro-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole and 100 ml-of 40% aqueous methylamine solution were placed. After sealing the vessel, the solution was stirred at 120° C. for 12 hours. After allowing to cool, the mixture was poured into water and was extracted with ether. The ether layer was washed three times with water and three times with saturated aqueous sodium chloride solution. The resultant was then dried over anhydrous sodium sulfate and then the resultant was concentrated, followed by purification by silica gel column chromatography to obtain 2.55 g of 3-(2,6-dichlorophenyl)-4-methylamino-1,2,5-thiadiazole.

m.p.: 145°-146° C.

¹ H-NMR (CDCl₃, δppm) 3.02 (s, 3H), 4.10 (bs, 1H), 7.15-7.4 (m, 3H).

IR (KBr, cm⁻¹) 3320, 1555, 1425, 790, 775.

MS (m/z): 259 (M⁺).

EXAMPLE 28 Preparation of 3-acetylamino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole (Compound No. 185)

To a solution containing 0.49 g of 3-amino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole and 0.22 g of triethylamine in N,N-diemthylformamide, 0.20 g of acetyl chloride was added and the mixture was stirred at 60° C. for 12 hours. After allowing to cool, the mixture was poured into water and was extracted with ether. The ether layer was washed twice with dilute hydrochloric acid, twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate, concentrated and purified by silica gel chromatography to obtain 0.25 g of 3-acetylamino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole.

m.p.: 180°-185° C.

¹ H-NMR (CDCl₃, δppm) 2.1 (s, 3H), 7.37 (s, 3H), 9.47 (bs, 1H).

IR (KBr, cm⁻¹) 3290, 1695, 1540, 1500, 1425, 1230, 785.

MS (m/z): 287 (M⁺).

EXAMPLE 29 Preparation of 3-(2,6-dichlorophenyl)-4-phthalimide-1,2,5-thiadiazole (Compound No. 186)

To a solution of 2.66 g of 3-chloro-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole in N,N-dimethylformamide, 2.22 g of potassium phthalimide was added and the mixture was heated to reflux at 110° C. for 12 hours. After allowing to cool, the mixture was poured into water and was extracted with ether. The ether layer was washed twice with dilute aqueous sodium hydroxide solution, twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography to obtain 1.90 g of 3-(2,6-dichlorophenyl)-4-phthalimide-1,2,5-thiadiazole.

m.p.: 214°-215° C.

¹ H-NMR (CDCl₃, δppm) 7.15-7.4 (m, 3H), 7.55-7.95 (m, 4H).

IR (KBr, cm⁻¹) 1790, 1745, 1730, 1470, 1465, 1430, 1415, 1310, 710.

MS (m/z): 375 (M⁺).

EXAMPLE 30 Preparation of 3-(2,6-dichlorophenyl)-4(3,3-dimethylureido)-1,2,5-thiadiazole (Compound No. 187)

To a solution of 0.49 g of 3-amino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole and 0.22 g of triethylamine in N,N-dimethylformamide, 0.24 g of dimethylcarbamoyl chloride was added and the mixture was heated at 120° C. for 12 hours. After allowing to cool, the mixture was poured into water and was extracted with ether. The ether layer was washed twice with dilute hydrochloric acid, twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography to obtain 0.19 g of 3-(2,6-dichlorophenyl)-4(3,3-dimethylureido)-1,2,5-thiadiazole.

m.p.: 100°-103° C.

¹ H-NMR (CDCl₃, δppm) 2.83 (s, 3H), 3.00 (s, 3H), 7.15-7.45 (m, 3H), 8.27 (s, 1H).

IR (KBr, cm⁻¹) 1630, 1460, 1425, 1380, 1115, 1100, 790, 775.

MS (m/z): 316 (M⁺).

EXAMPLE 31 Preparation of 3-isobutyrylamino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole (Compound No. 188)

To a solution of 0.49 g of 3-amino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole and 0.22 g of triethylamine in N,N-dimethylformamide, 0.27 g of isobutyryl chloride was added and the mixture was heated at 60° C. for 12 hours. After allowing to cool, the mixture was poured into water and was extracted with ether. The ether layer was washed twice with dilute hydrochloric acid, twice with water and twice with saturated aqueous sodium chloride solution. The resultant was dried over anhydrous sodium sulfate, concentrated and purified by silica gel column chromatography to obtain 0.23 g of 3-isobutyrylamino-4-(2,6-dichlorophenyl)-1,2,5-thiadiazole

m.p.: 112°-117° C.

¹ H-NMR (CDCl₃, δppm) 1.08 (d, J=7Hz, 6H), 2.68 (septet, J=7Hz, 1H) 7.2-7.45 (m, 3H), 8.10 (bs, 1H).

IR (KBr, cm⁻¹) 3290, 1700, 1540, 1495, 1430, 1145.

MS (m/z): 315 (M⁺).

EXAMPLE 32 Test for Evaluation of Effectiveness in Growth Inhibition of Weeds by Treatment of Water in Paddy Field

The compounds with Compound Nos. 183-188 formulated into wettable powder according to Example 9 were tested for their effectiveness in growth inhibition of weeds in the same manner as in Example 12. The results are shown in Table 6.

                                      TABLE 1                                      __________________________________________________________________________                                                        Elementary Analysis:        Com-                          Prop-          IR    Found                       pound                         er- NMR (60MHz)                                                                               (cm.sup.-1,                                                                          (Calcd.) %                  No. X   V   Z   Y A           ties                                                                               (δ ppm, CDCl.sub.3)                                                                 KBr)  C   H   N                   __________________________________________________________________________     1   H   3-Cl                                                                               4-Cl                                                                               O H           m.p. 235˜ 240° C.                                                      ##STR20## 3200-2400, 1525, 1225, 890,                                                    855, 830                                                                             (39.24 (38.88)                                                                     1.82 (1.63)                                                                        11.38 (11.33)       2   H   3-Cl                                                                               4-Cl                                                                               O                                                                                 ##STR21##  m.p. 129˜ 130° C.                                                     3.00(s, 3H), 3.17(s, 3H), 7.46(d,                                              J=8Hz, 1H), 7.70(dd, J=8Hz, 2Hz, 1H),                                          7.97(d,  J=2Hz, 1H)                                                                       1745, 1370, 1140                                                                     41.80 (41.52)                                                                      2.99 (2.85)                                                                        13.15 (13.20)       3   H   2-Cl                                                                               4-Cl                                                                               O H           m.p. 166˜ 168° C.                                                      ##STR22## 3200-2400, 1585, 1530, 1230,                                                   885, 865, 825, 805                                                                   39.17 (38.88)                                                                      1.54 (1.63)                                                                        11.08 (11.33)       4   H   2-Cl                                                                               4-Cl                                                                               O                                                                                 ##STR23##  Vis- cose Oil                                                                      2.88(s, 3H), 2.98(s, 3H),                                                      7.1˜7.5(m, 3H)                                                                      1745, 1370 1150 (NaCl)                                                               41.89 (41.52)                                                                      2.99 (2.85)                                                                        12.80 (13.20)       5   H   3-Cl                                                                               4-Cl                                                                               O                                                                                 ##STR24##  m.p. 134˜ 135° C.                                                     1.8-2.3(m, 4H), 3.3- 3.9(m, 4H),                                               7.43(d, J=8Hz, 1H), 7.70(dd, J=8Hz,                                            2Hz, 1H), 7.93(d, J=2Hz,                                                                  1740, 1395, 1370, 1225,                                                        1065, 835, 740                                                                        45.30 (45.36)                                                                     3.41 (3.22)                                                                        12.16 (12.20)       6   H   2-Cl                                                                               4-Cl                                                                               O                                                                                 ##STR25##  Vis- cose Oil                                                                      1.7˜2.2(m, 4H), 3.2˜3.8(m,                                         4H), 7.2˜7.6(m,                                                                     1750, 1370, 1225, 1080, 1050                                                   NaCl) 45.31 (45.36)                                                                      3.41 (3.22)                                                                        12.15 (12.20)       8   H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR26##  m.p. 74˜ 75° C.                                                       1.6˜2.1(m, 4H), 3.2˜3.6(m,                                         4H), 7.2˜7.45(m,                                                                    1730, 1430, 1365, 1340,                                                        1230, 1160, 785                                                                      45.58 (45.36)                                                                      3.30 (3.22)                                                                        12.38 (12.20)       9   H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR27##  m.p. 105˜ 106° C.                                                     1.03(t, J=7Hz, 6H), 3.26(broad q, J=                                           7Hz, 4H), 7.2˜7.45 (m,                                                              1740, 1385, 1265, 1230,                                                        1210, 1145, 860,                                                                     44.96 (45.09)                                                                      3.95 (3.78)                                                                        11.93 (12.13)       10  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR28##  n.sub.D.sup.26.0 1.5633                                                            0.8˜1.7(m, 7H), 2.88(s, 3H),                                             3.0˜ 3.4(m, 2H), 7.2˜                                              7.45(m, 3H)                                                                               1740, 1430, 1385, 1230,                                                        1210, 1145, 790                                                                      47.02 (46.67)                                                                      3.99 (4.19)                                                                        11.52 (11.66)       12  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR29##  m.p. 103˜ 104° C.                                                     1.18(d, J=7Hz, 12H), 13.4˜4.3(m,                                         2H), 7.15˜7.4(m,                                                                    1740, 1430, 1300, 1230,                                                        1040, 1020, 960,                                                                     48.45 (48.13)                                                                      4.71 (4.57)                                                                        11.39 (11.22)       13  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR30##  m.p. 119˜ 120°                                                        1.2˜1.8(m, 6H), 3.1˜3.6(m,                                         4H), 7.2˜7.45(m,                                                                    1735, 1430, 1380, 1215,                                                        1140, 1020, 780                                                                      46.94 (46.93)                                                                      3.49 (3.65)                                                                        11.55 (11.72)       14  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR31##  m.p. 101˜ 102° C.                                                     0.9˜1.9(m, 10H), 2.75(s, 3H),                                            3.5˜ 4.1(m, 1H) 7.15˜                                              7.4(m, 3H) 2930, 1715, 1425, 1390,                                                        1355, 1315, 1220, 1140,                                                        1000, 800                                                                            49.86 (49.74)                                                                      4.52 (4.43)                                                                        11.18 (10.87)       15  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR32##  m.p. 98˜ 99° C.                                                       1.03(d, J=7Hz, 3H), 1.2˜1.8(m,                                           6H), 2.6˜3.2(m,                                                          1H), 3.7˜4.6(m,                                                          2H), 7.2˜7.45(m,                                                                    1730, 1435, 1420, 1390,                                                        1335, 1230, 1180, 1140,                                                        1040, 785                                                                            48.70 (48.39)                                                                      4.01 (4.06)                                                                        11.15 (11.28)       16  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR33##  m.p. 113˜ 116° C.                                                     1.06(d, J=7Hz, 6H), 1.3˜1.7(m,                                           6H), 3.9˜4.5(m,                                                          2H), 7.15˜7.4(m,3H)                                                                 1725, 1390, 1335, 1300,                                                        1225, 1060, 1030,785                                                                 49.87 (49.74)                                                                      4.27 (4.43)                                                                        10.72 (10.87)       17  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR34##  m.p. 134˜ 136° C.                                                     3.27(s, 6H), 7.2˜ 7.45(m,                                                           1550, 1425, 1385, 1275,                                                        1220, 1100, 790,                                                                     39.73 (39.52)                                                                      2.86 (2.71)                                                                        12.87 (12.57)       18  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR35##  m.p. 91˜ 93° C.                                                       3.23(s, 3H), 3.70(s, 3H),                                                      6.4˜7.4(m, 7H)                                                                      1745, 1600, 1590, 1430,                                                        1355, 1230, 1120,                                                                    50.08 (49.76)                                                                      3.98 (3.19)                                                                        10.61 (10.24)       19  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR36##  m.p. 107˜ 108° C.                                                     2.37(s, 3H), 7.0˜ 7.4(m, 5H),                                            7.70(d, J=8Hz, 2H)                                                                        1390, 1195, 1180, 830, 740,                                                    580, 545                                                                             44.99 (44.89)                                                                      2.54 (2.51)                                                                        6.88 (6.98)         20  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR37##  m.p. 101˜ 103° C.                                                     5.57(s, 2H), 7.1˜ 7.9(m,                                                            1700, 1480, 1430, 1395,                                                        1225, 790                                                                            52.49 (52.61)                                                                      2.86 (2.75)                                                                        7.92 (7.67)         21  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.3    m.p. 53˜ 55° C.                                                       4.03(s, 3H), 7.1˜ 7.35(m,                                                            ##STR38##                                                                           41.32 (41.39)                                                                      2.11 (2.31)                                                                        10.97 (10.72)       22  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR39##  m.p. 70˜ 71° C.                                                       5.40(s, 2H), 7.0˜ 7.4(m,                                                            1520, 1480, 1430, 1365,                                                        1310, 1245, 965, 790, 780,                                                     750, 700                                                                             53.41 (53.42)                                                                      2.99 (2.98)                                                                        8.17 (8.30)         23  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR40##  m.p. 52˜ 55° C.                                                       3.13(s, 3H), 3.57(s, 3H),                                                      7.1˜7.35(m, 3H)                                                                     1750, 1430, 1360, 1230,                                                        1115, 790                                                                            39.24 (39.53)                                                                      2.54 (2.71)                                                                        12.31 (12.57)       24  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR41##  m.p. 92˜ 94° C.                                                       3.2˜3.8(m, 8H), 7.15˜7.4(m,                                        3H)        1755, 1730, 1430, 1390,                                                        1210, 1120, 1050                                                                     43.57 (43.34)                                                                      2.95 (3.07)                                                                        11.28 (11.66)       25  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.2 CHCH.sub.2                                                                         n.sub.D.sup.26.2 1.5921                                                           4.8˜5.6(m, 4H), 5.7˜6.3(m,                                         1H) 7.1˜7.4(m, 3H)                                                                   ##STR42##                                                                           46.21 (46.00)                                                                      2.92 (2.80)                                                                        9.69 (9.75)         26  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.2 CCH                                                                               m.p. 90˜ 91° C.                                                       2.47(t, J=2Hz, 1H), 4.98(d, J=2Hz, 2H),                                        .1˜7.35(m, 3H)                                                                       ##STR43##                                                                           46.52 (46.33)                                                                      2.22 (2.12)                                                                        10.09 (9.82)        27  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR44##  m.p. 176˜ 177° C.                                                     1.52(d, J=7Hz, 3H), 5.25(q, J=Hz, 1H),                                         6.63(broad s, 1H), 7.40(s,                                                     3H) (acetone-d.sub.6)                                                                     3200-2500, 1730, 1480, 1430,                                                   1235, 790,                                                                           41.20 (41.39)                                                                      2.59 (2.52)                                                                        8.81 (8.77)         28  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.2 COOH                                                                              m.p. 156˜ 157° C.                                                      ##STR45## 3200-2400, 1735, 1485, 1430,                                                   1395, 1260,                                                                          39.20 (39.36)                                                                      1.84 (1.98)                                                                        8.99 (9.18)         29  H   2-F 6-F O H           m.p. 165˜ 166° C.                                                      ##STR46## 3300-2500, 1470, 1005,                                                               44.96 (44.86)                                                                      1.73 (1.88)                                                                        13.09 (13.07)       30  H   2-F 5-F O H           m.p. 180˜ 181° C.                                                      ##STR47## 3300-2500, 1480, 1470, 1250,                                                   1185, 880,                                                                           45.22 (44.86)                                                                      1.84 (1.88)                                                                        12.89 (13.07)       31  H   2-F 4-F O H           m.p. 181˜ 184° C.                                                      ##STR48## 3300-2500, 1535, 1470, 1260,                                                   1150, 880,                                                                           45.12 (44.86)                                                                      1.74 (1.88)                                                                        12.93 (13.07)       32  H   3-F 4-F O H           m.p. 205˜ 208° C.                                                      ##STR49## 3300-2400, 1525, 1425, 1285,                                                   1260, 875                                                                            44.60 (44.86)                                                                      2.07 (1.88)                                                                        13.35 (13.07)       33  H   2-F 6-F O                                                                                 ##STR50##  m.p. 77˜ 78° C.                                                       2.90(s, 3H), 2.98(s, 3H),                                                      6.7˜7.6(m, 3H)                                                                      1740, 1630, 1465, 1375,                                                        1230, 1150, 1005                                                                     46.16 (46.31)                                                                      3.27 (3.17)                                                                        14.67 (14.73)       34  H   2-F 5-F O                                                                                 ##STR51##  m.p. 86˜ 87° C.                                                       2.93(s, 3H), 3.07(s, 3H),                                                      6.9˜7.5(m, 3H)                                                                      1725, 1465, 1370, 1260,                                                        1175, 1150, 870, 825,                                                                46.26 (46.31)                                                                      3.30 (3.17)                                                                        15.10 (14.73)       36  H   2-F 4-F O                                                                                 ##STR52##  n.sub.D.sup.26.2 1.5542                                                            2.93(s, 3H), 3.05(s, 3H),                                                      6.7˜7.2(m, 2H), 7.4˜7.85(m,                                        H)         1745, 1425, 1375, 1270,                                                        1250, 1145, (NaCl)                                                                   45.99 (46.31)                                                                      3.32 (3.17)                                                                        14.96 (14.73)       37  H   3-F 4-F O                                                                                 ##STR53##  m.p. 76˜ 77° C.                                                       3.03(s, 3H), 3.17(s, 3H),                                                      6.9˜7.9(m, 3H)                                                                      1745, 1530, 1370, 1150,                                                              46.10 (46.31)                                                                      3.15 (3.17)                                                                        14.80 (14.73)       39  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR54##  m.p. 59˜ 60° C.                                                       1.27(d, J=6Hz, 6H), 4.90(septet, J=6Hz,                                        H), 7.2˜7.5(m, 3H                                                                   1780, 1430, 1250, 1220,                                                        1100, 910                                                                             45.56 (45.44)                                                                     3.17 (3.17)                                                                        8.76 (8.83)         40  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR55##  n.sub.D.sup.23.8 1.5669                                                            1.08(d, J=7Hz, 6H), 2.68(septet, J=7Hz,                                        H), 7.2˜7.5(m, 3H)                                                                  1780, 1460, 1430, 1395,                                                        1170, 1115, 790 (NaCl)                                                               43.27 (43.25)                                                                      2.95 (3.02)                                                                        8.17 (8.40)         41  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.2 OCH.sub.3                                                                         n.sub.D.sup.23.9 1.5868                                                            3.48(s, 3H), 5.50(s, 2H),                                                      7.2˜7.45(m, 3H)                                                                      ##STR56##                                                                           41.19 (41.25)                                                                      2.60 (2.76)                                                                        9.44 (9.62)         42  H   3-F 5-F O H           m.p. 234˜ 136° C.                                                      ##STR57## 3300-2300, 1600, 1450, 1320,                                                   1120, 990,                                                                           45.10 (44.86)                                                                      1.85 (1.88)                                                                        13.31 (13.07)       43  H   2-Cl                                                                               6-Cl                                                                               O S.sub.1 (CH.sub.3).sub.3                                                                   n.sub.D.sup.23.8 1.5488                                                            0.33(s, 9H), 7.2˜ 7.45(m,                                                            ##STR58##                                                                           40.99 (41.38)                                                                      3.87 (3.78)                                                                        8.64 (8.77)         44  H   3-F 5-F O                                                                                 ##STR59##  m.p. 65˜ 66° C.                                                       3.02(s, 3H), 3.17(s, 3H), 6.83(tt,                                             J=8Hz, 2Hz, 1H), 7.2˜7.7 (m,                                                        1725, 1600, 1380, 1305,                                                        1150, 1130, 990                                                                      46.40 (46.31)                                                                      3.05 (3.17)                                                                        14.80 (14.73)       45  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR60##  m.p. 75˜ 77° C.                                                       3.85(s, 3H), 7.2˜ 7.5(m,                                                            1785, 1775, 1430, 1250,                                                        1225, 780                                                                            39.10 (39.36)                                                                      1.85 (1.98)                                                                        9.41 (9.18)         46  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR61##  n.sub.D.sup. 26.2 1.5690                                                           1.27(t, J=7Hz, 3H), 4.27(q, J=7Hz, 2H),                                        .2˜7.5(m, 3H)                                                                       1785, 1430, 1245, 1215,                                                        1010, 790 (NaCl)                                                                     41.77 (41.39)                                                                      2.57 (2.52)                                                                        8.77 (8.77)         47  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR62##  m.p. 95˜ 96° C.                                                       1.43(s, 9H), 7.2˜ 7.45(m,                                                           1775, 1270, 1255, 1230,                                                        1145, 1115, 900,790                                                                  44.75 (44.97)                                                                      3.40 (3.48)                                                                        7.78 (8.06)         48  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR63##  Vis- cose Oil                                                                      5.2(s, 2H), 7.2˜ 7.5(m,                                                             1785, 1265, 1215 (NaCl)                                                              50.79 (50.40)                                                                      2.82 (2.64)                                                                        6.98 (7.34)         49  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR64##  Vis- cose Oil                                                                      6.9˜7.6(m)                                                                          1800, 1240, 1215, 1190                                                         (NaCl)                                                                               48.80                                                                              2.02 (2.19)                                                                        7.52 (7.62)         50  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR65##  m.p. 46˜ 48° C.                                                       3.33(s, 3H), 3.45˜ 3.7(m, 2H),                                           4.25˜ 4.55(m, 2H), 7.2˜                                            7.5(m, 3H) 1785, 1225, 1200                                                                     40.95 (41.27)                                                                      2.73 (2.88)                                                                        8.81 (8.02)         51  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR66##  m.p. 114˜ 115° C.                                                     4.80(s, 2H), 7.2˜ 7.5(m,                                                            1795, 1435, 1400, 1215, 790,                                                   760, 725                                                                             31.64 (31.27)                                                                      1.36 (1.19)                                                                        6.60 (6.63)         52  H   2-Cl                                                                               6-Cl                                                                               O C.sub.3 H.sub.7.sup.1                                                                      n.sub.D.sup.26.0 1.5747                                                            1.33(d, J=6Hz, 6H), 5.17(septet, J=6Hz,                                        H), 7.15˜7.45(m, 3H)                                                                 ##STR67##                                                                           45.54 (45.68)                                                                      3.34 (3.48)                                                                        9.64 (9.68)         53  H   2-Cl                                                                               6-Cl                                                                               O C(CH.sub.3).sub.3                                                                          n.sub.D.sup.26.0 1.5658                                                            1.53(s, 9H), 7.2˜ 7.45(m,                                                            ##STR68##                                                                           47.61 (47.53)                                                                      4.12 (3.98)                                                                        9.13 (9.23)         54  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR69##  m.p. 68˜ 69° C.                                                       0.30(s, 6H), 0.82(s, 9H),                                                      7.2˜7.45(m, 3H)                                                                     1485, 1475, 1435, 1255, 860,                                                   845, 795                                                                             46.23 (46.53)                                                                      4.82 (5.02)                                                                        7.96 (7.75)         55  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR70##  m.p. 83˜ 86° C.                                                       1.13(s, 9H), 7.2˜ 7.4(m,                                                            1765, 1430, 1395, 1085, 790,                                                   780   46.78 (47.14)                                                                      3.59 (3.65)                                                                        8.51 (8.45)         56  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR71##   n.sub.D.sup.26.0 1.5657                                                            ##STR72## 1490, 1435, 1380, 1120,                                                        1110, 930 (NaCl)                                                                     43.35 (42.99)                                                                      3.65 (3.60)                                                                        8.04 (8.35)         57  H   2-Cl                                                                               6-Cl                                                                               O CH.sub.2 SCH.sub.3                                                                         m.p. 81˜ 82° C.                                                       2.22(s, 3H), 5.47(s, 2H),                                                      7.2˜7.5(m, 3H)                                                                       ##STR73##                                                                           38.80 (39.09)                                                                      2.45 (2.62)                                                                        9.42 (9.11)         58  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR74##  m.p. 118˜ 120° C.                                                     5.87(s, 2H), 7.1˜ 7.7(s, 6H),                                            7.8˜ 8.2(m, 1H)                                                                     1535, 1485, 1430, 1355,                                                              47.39 (47.13)                                                                      2.19 (2.37)                                                                        10.98 (10.99)       59  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR75##   m.p. 50˜ 51° C.                                                      5.60(s, 2H), 7.0˜ 7.8(m, 6H),                                            8.4˜ 8.6(m, 1H)                                                                     1490, 1430, 1415, 1365,                                                        1250, 785, 750                                                                       49.54 (49.71)                                                                      2.65 (2.68)                                                                        12.68 (12.42)       60  H   2-Cl                                                                               6-Cl                                                                               O SO.sub.2 CH.sub.3                                                                          m.p. 78˜ 80° C.                                                       3.45(s, 3H), 7.2˜ 7.5(m,                                                             ##STR76##                                                                           33.00 (33.24)                                                                      1.73 (1.85)                                                                        8.50 (8.61)         61  H   2-Cl                                                                               6-Cl                                                                               O SO.sub.2 CF.sub.3                                                                          n.sub.D.sup.26.0 1.5303                                                            7.25˜7.5(m)                                                                          ##STR77##                                                                           28.55 (28.51)                                                                      0.77 (0.79)                                                                        7.66 (7.38)         63  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR78##  n.sub.D.sup.26.3 1.5560                                                            1.12(t, J=7Hz, 3H), 1.4˜2.0(m,                                           2H), 2.92(broad s, 3H), 3.1˜3.7(m,                                        6H),  7.2˜7.5(m,                                                                   1750, 1435, 1385, 1235,                                                        1200, 1115, 790 (NaCl)                                                               46.55 (46.16)                                                                      4.37 (4.39)                                                                        10.36 (10.76)       64  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR79##  n.sub.D.sup.26.6 1.5715                                                            4.5˜4.8(m, 2H), 5.0˜6.2(m,                                         3H), 7.2˜7.5(m,                                                                     1785, 1430, 1215, (NaCl)                                                             43.41 (43.52)                                                                      2.50 (2.43)                                                                        8.44 (8.45)         65  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR80##  m.p. 57˜ 58° C.                                                       0.87(d, J=7Hz, 6H), 1.6˜2.3(m,                                           1H), 4.00(d, J=7Hz, 2H), 7.2˜7.5(m                                       , 3H)      1785, 1435, 1215                                                                     45.08 (44.97)                                                                      3.63 (3.48)                                                                        8.36 (8.06)         67  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR81##  m.p. 67˜ 68° C.                                                       0.7˜1.2(m, 4H), 1.3˜1.9(m,                                         1H), 7.2˜7.5(m,                                                                      1765, 1375, 1125, 1085,                                                             46.10 (45.73)                                                                      2.44 (2.55)                                                                        8.82 (8.88)         68  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR82##  Vis- cose Oil                                                                      1.97(s, 3H), 2.00(s, 3H),                                                      7.2˜7.5(m, 3H)                                                                      1820-1780, 1560, 1430, 1400,                                                   1280, 1240-1160 (NaCl)                                                               41.44 (41.63)                                                                      2.58 (2.62)                                                                        11.99 (12.13)       69  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR83##  Vis- cose Oil                                                                      1.5˜2.2(m, 4H), 3.6˜4.4(m,                                         5H), 7.2˜7.5(m,                                                                     1785, 1435, 1220 (NaCl)                                                              44.76 (44.81)                                                                      3.41 (3.22)                                                                        7.54 (7.46)         70  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR84##  Vis-  cose Oil                                                                     2.30(s, 3H), 3.43(s, 3H), 3.80(s, 3H),                                         6.30(s, 1H), 7.2˜ 7.5(m,                                                            1755, 1600, 1560, 1435,                                                        1365, 1100 (NaCl)                                                                    45.32 (45.08)                                                                      3.05 (3.07)                                                                        16.68 (16.42)       71  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR85##  m.p. 111˜ 112° C.                                                     7.2˜8.2(m)                                                                          1750, 1225, 1060                                                                     50.92 (51.29)                                                                      2.33 (2.29)                                                                        8.29 (7.97)         72  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR86##  m.p. 99˜ 100° C.                                                      7.15˜7.4(m, 3H), 7.8˜8.0(m,                                        1H), 8.15˜8.35(m,                                                                   1390, 1330, 1295, 1155,                                                        1140, 1070                                                                           39.57 (39.41)                                                                      1.23 (1.18)                                                                        9.98 (9.84)         73  H   2-Me                                                                               6-Me                                                                               O H           m.p. 134˜ 135° C.                                                     2.13(s, 6H), 6.8- 7.4(m,                                                                   ##STR87##                                                                           58.42 (58.23)                                                                      4.91 (4.88)                                                                        13.82 (13.58)       74  2-Cl                                                                               3-Cl                                                                               6-Cl                                                                               O H           m.p. 157˜ 160° C.                                                      ##STR88## 3300-2400, 1535, 1495, 1220,                                                   1180, 815,                                                                           34.48 (34.12)                                                                      1.02 (1.07)                                                                        9.83 (9.94)         76  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR89##  m.p. 104˜ 106° C.                                                     7.1˜7.5(m, 6H), 7.7˜8.0(m,                                         1H)        1770, 1230, 1140                                                                     46.81 (46.71)                                                                      1.83 (1.82)                                                                        7.60 (7.26)         77  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR90##  m.p. 83˜ 86° C.                                                       7.0˜7.7(m, 5H), 7.7˜8.0(m,                                         2H)        1775, 1760, 1225                                                                     46.47 (46.71)                                                                      1.66 (1.82)                                                                         7.10 (7.26)        78  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR91##  m.p. 137˜ 138° C.                                                     7.2˜7.6(m, 5H), 7.93(d, J=8Hz,                                           2H)        1770, 1230, 1150                                                                     46.51 (46.71)                                                                      1.76 (1.82)                                                                        7.58 (7.26)         79  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR92##  m.p. 131˜ 133° C.                                                     7.2˜7.4(m, 3H), 8.1˜8.3(m,                                         4H)        1765, 1530, 1230,                                                                    45.85 (45.47)                                                                      1.82 (1.78)                                                                        10.73 (10.60)       80  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR93##  m.p. 138˜ 140° C.                                                     7.25˜7.5(m, 3H), 7.75(d, J=8Hz,                                          2H), 8.10(d, J=8Hz, 2H)                                                                   2240, 1760, 1260, 1230,                                                              51.41 (51.08)                                                                      2.06 (1.87)                                                                        11.08 (11.16)       81  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR94##  m.p. 140˜ 141° C.                                                     2.37(s, 3H), 7.0˜ 7.3(m, 5H),                                            7.80(d, J=8Hz, 2H)                                                                        1755, 1270, 1185,                                                                    52.22 (52.61)                                                                      2.79 (2.75)                                                                        7.50 (7.67)         82  H   2-Cl                                                                               6-F O H           m.p. 142˜ 144° C.                                                      ##STR95## 3300˜2500, 1535, 1520,                                                   510, 1445, 1230,                                                                     41.73 (41.66)                                                                      1.88 (1.74)                                                                        12.46 (12.14)       83  H   2-Cl                                                                               6-F O                                                                                 ##STR96##  m.p. 67˜ 68° C.                                                       2.88(s, 3H), 2.97(s, 3H),                                                      6.8˜7.5(m, 3H)                                                                      1750, 1375, 1150 (NaCl)                                                              43.63 (43.78)                                                                      3.04 (3.00)                                                                        13.65 (13.92)       84  H   2-Cl                                                                               6-F O                                                                                 ##STR97##  Vis-  cose Oil                                                                     1.13(d, J=7Hz, 6H), 2.70(septet, J=7Hz,                                        H), 6.8˜7.4(m, 3H)                                                                  1780, 1455, 1405, 1080                                                         (NaCl)                                                                               47.72 (47.92)                                                                      3.54 (3.35)                                                                        9.21 (9.31)         85  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR98##  m.p. 105˜ 106° C.                                                     3.83(s, 3H), 6.87(d, J=9Hz, 2H),                                               7.1˜ 7.4(m, 3H), 7.92(d, J=9Hz,                                          2H)        1745, 1260, 1170                                                                     50.38 (50.40)                                                                      2.50 (2.64)                                                                        7.34 (7.34)         86  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR99##  Vis- cose Oil                                                                      0.80(t, J=7Hz, 3H), 1.2˜1.9(m,                                           2H) 2.43(t, J=7Hz, 2H), 7.3˜7.5(m,                                        3H)       1790, 1440, 1400, 1235, 1085                                                   NaCl) 45.33 (45.44)                                                                      3.09 (3.17)                                                                        9.09 (8.83)         87  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR100## Vis- cose Oil                                                                      0.6˜1.9(m, 7H), 2.43(t, J=7Hz,                                           2H, 7.2˜7.5(m, 3H)                                                                  1790, 1435, 1400, 1080,                                                        (NaCl)                                                                               47.18 (47.14)                                                                      3.64 (3.65)                                                                        8.47 (8.45)         88  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR101## n.sub.D.sup.25.2 1.5592                                                            0.82(d, J=6Hz, 6H), 1.5˜2.5(m,                                           3H), 7.2˜7.5(m,                                                                     1785, 1435, 1400, 1080                                                         (NaCl)                                                                               47.48 (47.14)                                                                      3.77 (3.65)                                                                        8.60 (8.45)         89  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR102## m.p. 100˜ 101° C.                                                     7.1˜7.5(m, 4H), 7.5˜8.3(m,                                         3H)        1775, 1760, 1435, 1230,                                                              42.23 (41.88)                                                                      1.57 (1.64)                                                                        6.50 (6.51)         90  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR103## m.p. 87˜ 88° C.                                                       2.37(s, 3H), 7.1˜ 7.5(m, 5H),                                            7.6˜ 7.9(m, 2H)                                                                     1755, 1265, 1230, 1190,                                                              52.54 (52.61)                                                                      2.94 (2.75)                                                                        7.65 (7.67)         91  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR104## m.p. 102˜ 103° C.                                                     7.2˜7.4(m, 3H), 7.63(t, J=8Hz,                                           1H), 8.2˜8.6(m, 2H), 8.78(t,                                             J=2Hz, 1H) 1760, 1535, 1225                                                                     45.07 (45.47)                                                                      1.61 (1.78)                                                                        10.27 (10.60)       92  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR105## m.p. 91˜ 93° C.                                                       7.1˜7.9(m)                                                                          1765, 1270, 1230, 1180,                                                              49.01 (48.79)                                                                      2.03 (1.91)                                                                        7.29 (7.58)         93  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR106## m.p. 121˜ 122° C.                                                     7.2˜7.5(m, 3H), 7.55(t, J=1.5Hz,                                         1H), 7.86(d, J=1.5 Hz,                                                                    1760, 1435, 1250,                                                                    42.63 (42.88)                                                                      1.51 (1.43)                                                                        6.91 (6.66)         94  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR107## m.p. 84˜ 85° C.                                                       7.2˜8.0(m, 5H), 8.1˜8.4(m,                                         2H)        1770, 1330, 1220, 1170,                                                        1135, 1075, 1060                                                                     45.46 (45.84)                                                                      1.77 (1.68)                                                                        6.41 (6.68)         95  H   2-Cl                                                                               6-Cl                                                                               0                                                                                 ##STR108## m.p. 144˜ 146° C.                                                     7.2˜8.0(m, 5H), 8.1˜8.4(m,                                         2H)        2215, 1765, 1430, 1395,                                                        1260, 1230, 1160,                                                                    51.07 (51.08)                                                                      1.94 (1.87)                                                                        11.27 (11.16)       96  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR109## m.p. 78˜ 80° C.                                                       3.78(s, 3H), 7.0˜ 7.7(m,                                                            1690, 1315, 1295                                                                     50.01 (50.40)                                                                      2.74 (2.64)                                                                        6.97 (7.34)         97  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR110## m.p. 133˜ 136° C.                                                     3.27(s, 3H), 4.73 (s, 2H),                                                     7.1˜7.5 (m, 8H)                                                                     1675, 1520, 1485,                                                                    51.68 (51.78)                                                                      3.12 (3.32)                                                                        10.29 (10.65)       98  H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR111## m.p. 118˜ 121° C.                                                     5.02(s, 2H), 7.0˜ 7.6(m, 8H),                                            7.93(bs,  1H)                                                                             1680, 1485, 1410                                                                     50.17 (50.54)                                                                      2.85 (2.91)                                                                        11.23 (11.05)       99  2-MeO                                                                              3-Cl                                                                               6-MeO                                                                              O H           m.p. 118˜ 120° C.                                                      ##STR112##                                                                               3400˜2600, 1540, 1470,                                                   295, 1230, 1100                                                                      44.29 (44.04)                                                                      3.16 (3.32)                                                                        9.88 (10.27)        100 H   2-Cl                                                                               5-Cl                                                                               O H           m.p. 117˜ 118° C.                                                      ##STR113##                                                                               3200˜2400, 1540, 1455,                                                   110, 810                                                                             39.09 (38.88)                                                                      1.62 (1.63)                                                                        11.10 (11.33)       101 H   2-Cl                                                                               6-Me                                                                               O H           m.p. 131˜ 132° C.                                                      ##STR114##                                                                               3300˜2400, 1505,                                                               47.50 (47.68)                                                                      3.15 (3.11)                                                                        12.36 (12.35)       102 H   2-Cl                                                                               5-Cl                                                                               O                                                                                 ##STR115## m.p. 87˜ 90° C.                                                       2.93(s, 6H), 7.2˜ 7.5(m,                                                            1730, 1665, 1095                                                                     41.73 (41.52)                                                                      2.71 (2.85)                                                                        13.57 (13.20)       103 H   2-Cl                                                                               6-Me                                                                               O                                                                                 ##STR116## m.p. 89˜ 90° C.                                                       2.13(s, 3H), 2.80(s,  3H), 2.90(s, 3H),                                        .0˜7.3(m, 3H)                                                                       1745, 1370, 1150                                                                     48.64 (48.40)                                                                      4.13 (4.06)                                                                        13.72 (14.11)       105 2-Cl                                                                               3-NO.sub.2                                                                         6-Cl                                                                               O H           m.p. 192˜ 194° C.                                                      ##STR117##                                                                               3200˜2400, 1535, 1350,                                                   70    33.13 (32.89)                                                                      1.07 (1.03)                                                                        14.37 (14.38)       106 2-Cl                                                                               3-NO.sub.2                                                                         6-Cl                                                                               O                                                                                 ##STR118## Vis- cose Oil                                                                      2.13(d, J=7Hz, 6H), 2.73(septet, J=7Hz,                                        H), 7.57(d, J=9Hz, 1H), 7.88(d, J=9Hz,                                         1H)        1780, 1540, 1370, 1350, 1070                                                   (NaCl)                                                                               39.78 (39.79)                                                                      2.48 (2.50)                                                                        11.34 (11.60)       107 2-Cl                                                                               3-NO.sub.2                                                                         6-Cl                                                                               O                                                                                 ##STR119## m.p. 93˜ 95° C.                                                       2.90(s, 3H), 2.98 (s, 3H), 7.53(d, J=                                          8.5Hz, 1H), 7.83(d, J=8.5Hz,                                                              1735, 1540, 1360,                                                                    36.18 (36.37)                                                                      2.11 (2.22)                                                                        15.37 (15.42)       108 H   2-F 6-F O                                                                                 ##STR120## m.p. 39˜ 41° C.                                                       3.84(s, 3H), 6.75˜ 7.65(m,                                                          1790, 1470, 1260, 1225,                                                              43.86 (44.12)                                                                      2.24 (2.22)                                                                        10.36 (10.29)       109 H   3-F 4-F O                                                                                 ##STR121## m.p. 49˜ 50° C.                                                       3.97(s, 3H), 7.20(m, 1H), 7.73(m,                                                         1880, 1790, 1530, 1430,                                                        1290, 1275, 1240,                                                                    44.25 (44.12)                                                                      2.03 (2.22)                                                                        10.14 (10.29)       110 2-F 3-NO.sub.2                                                                         6-F O                                                                                 ##STR122## m.p. 90˜ 92° C.                                                       3.90(s, 3H), 7.18 (ddt, J- 1, 5Hz, 8Hz,                                        Hz, 1H), 8.24(ddt, J=5,5Hz, 9Hz, 9Hz,                                          1H)        1805, 1795, 1540, 1360,                                                        1250, 1220, 1190                                                                     37.89 (37.86)                                                                      1.41 (1.58)                                                                        13.38 (13.24)       111 2-F 3-NO.sub.2                                                                         6-F O H           m.p. 152˜ 154° C.                                                      ##STR123##                                                                               3300˜2500, 1535, 1475,                                                   360   37.06 (37.07)                                                                      1.16 (1.16)                                                                        15.90 (16.21)       112 2-NO.sub.2                                                                         4-F 5-F O                                                                                 ##STR124## n.sub.D.sup.26.1 1.5560                                                            3.87(s, 3H), 7.2˜ 7.6(m, 1H),                                            7.98(dd, J=7Hz, 9Hz, 1H)                                                                  1790, 1550, 1350, 1305,                                                        1250, 1225, 1210,                                                                    37.91 (37.86)                                                                      1.58 (1.58)                                                                        13.57 (13.24)       113 2-NO.sub.2                                                                         3-F 4-F O H           m.p. 213˜ 214° C.                                                      ##STR125##                                                                               3200˜2400, 1550, 1520,                                                   345, 1320                                                                            36.83 (37.07)                                                                      1.01 (1.16)                                                                        16.44 (16.21)       114 H   2-NO.sub.2                                                                         3-CF.sub.3                                                                         O                                                                                 ##STR126## m.p. 82˜ 83° C.                                                       3.87(s, 3H), 7.7˜ 8.3(m,                                                            1790, 1535, 1220                                                                     37.61 (37.83)                                                                      1.85 (1.73)                                                                        12.26 (12.03)       115 H   2-NO.sub.2                                                                         5-CF.sub.3                                                                         O                                                                                 ##STR127## m.p. 41˜ 43° C.                                                       3.99(s3H), 7.8˜ 8.1(m, 1H),                                              8.2˜ 8.5(m, 2H)                                                                     1790, 1545, 1260,                                                                    38.07 (37.83)                                                                      1.67 (1.73)                                                                        12.30 (12.03)       116 H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR128## m.p. 93˜ 94° C.                                                       6.8˜7.6(m)                                                                          1490, 1435, 1390, 1290,                                                        1175, 790                                                                            46.60 (47.00)                                                                      2.09 (2.10)                                                                        7.11 (7.30)         117 H   2-Br                                                                               6-Cl                                                                               O H           m.p. 200˜ 205° C.                                                      ##STR129##                                                                               3300˜2400, 1535, 1510,                                                   430, 880, 770                                                                        32.76 (32.94)                                                                      1.26 (1.38)                                                                        9.79 (9.60)         118 H   2-NO.sub.2                                                                         5-CF.sub.3                                                                         O H           m.p. 211˜ 212° C.                                                      ##STR130##                                                                               3300˜2400, 1595, 1535,                                                   345, 1155, 1135                                                                      37.02 (37.12)                                                                      1.37 (1.38)                                                                        14.28 (14.42)       119 H   2-Br                                                                               6-Cl                                                                               O                                                                                 ##STR131## m.p. 77˜ 80° C.                                                       3.93(s, 3H), 7.0˜ 7.8(m,                                                            1770, 1440, 1260,                                                                    34.38 (34.35)                                                                      1.56 (1.72)                                                                        7.97 (8.01)         120 H   2-NO.sub.2                                                                         5-F O                                                                                 ##STR132## n.sub.D.sup.25.1 1.5762                                                            3.87(s, 3H), 7.0˜ 7.4(m, 2H),                                            8.13(dd, J=5Hz, 10Hz,                                                                     1790, 1590, 1530, 1440,                                                        1350, 1280, 1230, 1190                                                         (NaCl)                                                                               39.97 (40.13)                                                                      1.94 (2.02)                                                                        14.40 (14.04)       121 H   2-Cl                                                                               5-Cl                                                                               O                                                                                 ##STR133## n.sub.d.sup.25.2 1.5883                                                            3.87(s, 3H), 7.3˜ 7.5(m,                                                            1785, 1435, 1245, 1220,                                                        1100, 1020, 935 (NaCl)                                                               39.46 (39.36)                                                                      2.01 (1.98)                                                                        9.56 (9.18)         122 H   2-NO.sub.2                                                                         5-CF.sub.3                                                                         O                                                                                 ##STR134## m.p. 103˜ 104° C.                                                     3.04(s, 3H), 3.17(s, 3H), 7.94(d,                                              J=8Hz, 1H), 8.1˜8.4(m, 2H)                                                          1750, 1545, 1370,                                                                    40.01 (39.78)                                                                      2.46 (2.50)                                                                        15.14 (15.46)       123 H   2-NO.sub.2                                                                         5-Cl                                                                               O H           m.p. 194˜ 204° C.                                                      ##STR135##                                                                               3300˜2400, 1595, 1580,                                                   525, 1350, 850                                                                       39.75 (39.76)                                                                      1.49 (1.66)                                                                        17.19 (17.38)       124 H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR136## n.sub.D.sup.27.3 1.5748                                                            2.97(s, 6H), 7.3˜ 7.5(m,                                                            1430, 1390, 1180, 740                                                                33.72 (33.90)                                                                      2.67 (2.56)                                                                        12.07 (11.86)       125 H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR137## n.sub.D.sup.27.2 1.5741                                                            7.16(d, J=8.5Hz, 1H), 7.27(s, 3H),                                             7.90(dd, J= 2.5Hz, 8.5Hz, 1H), 8.42(bs,                                        H)         1610, 1390, 1325, 1245, 1130                                                   NaCl) 42.95 (42.87)                                                                      1.56 (1.54)                                                                        10.94 (10.71)       126 H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR138## m.p. 149˜ 154° C.                                                     7.0˜7.5(m)                                                                          1485, 1465, 1400,                                                                    47.22 (47.01)                                                                      1.92 (1.97)                                                                        7.75 (7.83)         127 H   2-Cl                                                                               6-Cl                                                                               O                                                                                 ##STR139## m.p. 89˜ 91° C.                                                       3.77(s, 3H), 6.7˜ 7.5(m,                                                            1505, 1465, 1400, 1240,                                                              51.36 (51.00)                                                                      2.66 (2.85)                                                                        7.97 (7.93)         128 3-Br                                                                               4-OH                                                                               5-Br                                                                               O CH.sub.3    m.p. 207˜ 210° C.                                                      ##STR140##                                                                               3350, 1405, 1395, 1245,                                                              29.31 (29.53)                                                                      1.53 (1.65)                                                                        7.67 (7.65)         129 H   2-NO.sub.2                                                                         5-F O                                                                                 ##STR141## m.p. 125˜ 126° C.                                                     2.89(s, 3H), 2.97(s, 3H),                                                      7.1˜7.5(m, 2H), 8.13(dd, J=4Hz,                                          9Hz, 1H)   1750, 1520, 1370, 1350,                                                              42.32 (42.30)                                                                      2.89 (2.90)                                                                        17.95 (17.94)       130 H   2-NO.sub.2                                                                         5-Cl                                                                               O                                                                                 ##STR142## n.sub.D.sup.25.2 1.5997                                                            3.88(s, 3H), 7.4˜ 7.7(m, 2H),                                            8.07(d, J=9Hz, 1H                                                                         1790, 1570,  1535, 1435,                                                       1345, 1250, 1220                                                                     38.16 (38.04)                                                                      2.01 (1.91)                                                                        13.38 (13.31)       __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________           Amount    Herbicidal Effect                                                    of Com-                                                                             Damage                                                                              Barn-                                                                              Small Flower                                               Compound                                                                             pound                                                                               to Crop                                                                             yard-                                                                              Umbrella-                                                                             Bul-                                                                              Mono-                                                                              Broad-                                       No.   g/10a                                                                               Rice grass                                                                              plant  rush                                                                              choria                                                                             leaved                                       __________________________________________________________________________     1     125  0    0   0      0  0   0                                                  250  0    0   0      0  0   0                                            2     125  0    2   4      2  5   4                                                  250  0    3   5      3  5   4                                            3     125  0    0   3      0  0   0                                                  250  0    1   5      0  0   3                                            4     125  0    1   5      1  5   4                                                  250  0    4   5      4  5   5                                            5     125  0    3   5      0  4   2                                                  250  0    4   5      0  5   2                                            6     125  0    2   4      2  --  2                                                  250  0    3   5      3  --  5                                            7     125  0    4.5 5      5  --  5                                                  250  0    5   5      5  --  5                                            8     125  0    5   5      3  --  5                                                  250  0    5   5      4  --  5                                            9     125  0    3   5      2  --  5                                                  250  0    4   5      2  --  5                                            10    125  0    4   5      2  --  5                                                  250  0    5   5      2  --  5                                            11    125  0    4   5      5  --  5                                                  250  0    5   5      5  --  5                                            12    125  0    3   5      2  --  3                                                  250  0    3   5      2  --  5                                            13    125  0    5   5      4.5                                                                               --  5                                                  250  0    5   5      5  --  5                                            14    125  0    3   5      2  --  5                                                  250  0    4   5      3  --  5                                            15    125  0    4   5      1  --  4                                                  250  0    4   5      2  --  5                                            16    125  0    4   5      2  --  2                                                  250  0    4   5      2  --  2                                            17    125  0    3   5      3  --  5                                                  250  0    4.5 5      3  --  5                                            18    125  0    3   5      2  --  5                                                  250  0    4.5 5      2  --  5                                            19    125  0    3   5      3  --  5                                                  250  0    4.5 5      3  --  5                                            20    125  0    3   3      2  --  0                                                  250  0    3   5      2  --  0                                            21    125  0    2   4      1  --  0                                                  250  0    2   4      1  --  3                                            22    125  0    2   5      3  --  2                                                  250  0    2   5      3  --  3                                            23    125  0    3   5      5  --  5                                                  250  0    4.5 5      5  --  5                                            24    125  0    4.5 5      4  --  5                                                  250  0    5   5      5  --  5                                            25    125  0    3   5      2  --  0                                                  250  0    3   5      2  --  0                                            26    125  0    4.5 5      1  --  2                                                  250  0    5   5      3  --  3                                            27    125  0    3   5      0  --  2                                                  250  0    3   5      0  --  2                                            28    125  0    3   5      2  --  5                                                  250  0    3   5      2  --  5                                            29    125  0    0   5      0  0   0                                                  250  0    0   5      1  0   0                                            30    125  0    0   0      2  0   0                                                  250  0    0   1      2  0   0                                            31    125  0    0   3      0  0   0                                                  250  0    0   5      1  0   0                                            32    125  0    0   0      2  0   0                                                  250  0    0   0      2  0   0                                            33    125  0    0   5      0  3   2                                                  250  0    2   5      2  3   5                                            34    125  0    3   5      1  1   2                                                  250  0    3   5      2  1   2                                            35    125  0    3   5      2  2   5                                                  250  0    3   5      2  2   5                                            36    125  0    2   5      0  0   2                                                  250  0    2   5      2  2   3                                            37    125  0    2   5      3  2   5                                                  250  0    4   5      4  5   5                                            38    125  0    0   2      0  0   2                                                  250  0    0   2      0  0   2                                            39    125  0    4   5      5  2   5                                                  250  0    4   5      5  2   5                                            40    125  0    3   5      5  5   5                                                  250  0    4.5 5      5  5   5                                            41    125  0    3   5      5  0   5                                                  250  0    4   5      5  5   5                                            42    125  0    1   4      0  2   0                                                  250  0    2   5      0  2   1                                            43    125  0    0   4      4  0   5                                                  250  0    2   4      4  1   5                                            44    125  0    3   4      2  2   4                                                  250  0    5   5      5  4   5                                            45    125  0    2   4      5  3   5                                                  250  0    4.5 5      5  3   5                                            46    125  0    4   3      5  1   5                                                  250  0    4   5      5  1   5                                            47    125  0    2   5      5  0   5                                                  250  0    5   5      5  2   5                                            48    125  0    3   3      5  0   5                                                  250  0    5   5      5  0   5                                            49    125  0    2   3      5  2   5                                                  250  1    4.5 5      5  2   5                                            50    125  0    3   0      5  1   5                                                  250  0    4   5      5  4   5                                            51    125  0    3   5      2  0   5                                                  250  0    4   5      5  1   5                                            52    125  0    0   5      0  0   0                                                  250  0    1   5      0  0   3                                            53    125  0    2   4      0  0   4                                                  250  0    2   4      0  0   4                                            54    125  0    1   5      4  0   5                                                  250  0    4.5 5      5  2   5                                            55    125  0    3   5      4  0   5                                                  250  0    4   5      5  5   5                                            56    125  0    2   5      1  4   5                                                  250  0    3   5      5  4   5                                            57    125  0    2   5      4  4   5                                                  250  0    4   5      5  4   5                                            58    125  0    2   4      0  0   1                                                  250  0    2   5      0  0   5                                            59    125  0    2   4      3  0   0                                                  250  0    2   5      3  0   2                                            60    125  0    4   4      5  0   5                                                  250  0    4.5 5      5  4   5                                            61    125  0    2   3      3  2   5                                                  250  0    4   5      5  2   5                                            62    125  0    0   4      0  0   0                                                  250  0    3   5      1  0   5                                            63    125  0    2   5      0  2   5                                                  250  0    4   5      1  2   5                                            64    125  0    2   5      5  2   5                                                  250  0    4   5      5  2   5                                            65    125  0    3   5      5  2   5                                                  250  0    3   5      5  2   5                                            66    125  0    2   5      5  3   5                                                  250  0    4   5      5  3   5                                            67    125  0    3   4      4  1   4                                                  250  0    4   5      5  4   5                                            68    125  0    1   3      4  3   5                                                  250  0    3   4      5  3   5                                            69    125  0    1   2      5  0   5                                                  250  0    3   5      5  3   5                                            70    125  0    4   5      5  1   5                                                  250  0    4.5 5      5  3   5                                            71    125  0    4.5 5      5  3   5                                                  250  0    5   5      5  5   5                                            72    125  0    4   5      0  0   3                                                  250  0    4   5      0  0   3                                            73    125  0    0   5      0  0   0                                                  250  0    4   5      0  0   0                                            74    125  0    3   5      0  2   0                                                  250  0    3   5      0  2   0                                            76    125  0    4   5      5  5   5                                                  250  0    5   5      5  5   5                                            77    125  0    5   5      5  5   5                                                  250  0    5   5      5  5   5                                            78    250  0    2   4      4  2   5                                                  500  0    4   5      5  4   5                                            79    125  0    5   5      5  5   5                                                  250  0    5   5      5  5   5                                            80    125  0    5   5      5  5   5                                                  250  0    5   5      5  5   5                                            81    125  0    2   5      4  2   5                                                  250  0    5   5      5  4   5                                            82    250  0    3   2      3  2   4                                                  500  0    4   2      4  3   5                                            83    250  0    3   3      3  3   5                                                  500  0    5   5      5  5   5                                            84    250  0    3   2      3  3   4                                                  500  0    5   2      5  4   5                                            85    125  0    4   5      5  4   5                                                  250  0    5   5      5  5   5                                            86    125  0    4   3      5  1   5                                                  250  0    4   5      5  2   5                                            87    125  0    4   5      4  1   5                                                  250  0    5   5      5  2   5                                            88    250  0    3   5      4  3   5                                                  500  0    5   5      5  5   5                                            89    250  0    4   5      5  5   5                                                  500  0    5   5      5  5   5                                            90    125  0    4   5      5  3   5                                                  250  0    4   5      5  5   5                                            91    250  0    4   5      5  3   5                                                  500  0    5   5      5  5   5                                            92    125  0    4   4      5  2   5                                                  250  0    5   5      5  3   5                                            93    250  0    3   5      3  2   5                                                  500  0    4   5      3  3   5                                            94    125  0    4   5      5  3   5                                                  250  0    5   5      5  4   5                                            95    250  0    2   5      4  2   5                                                  500  0    4   5      5  4   5                                            96    250  0    4   5      4  3   5                                                  500  0    5   5      5  3   5                                            97    250  0    3   5      3  1   4                                                  500  0    5   5      3  2   5                                            98    250  0    2   3      0  2   4                                                  500  0    3   5      1  3   4                                            99    250  0    3   3      1  3   3                                                  500  0    5   4      3  3   4                                            100   250  0    3   4      3  4   5                                                  500  0    4   5      4  4   5                                            101   250  0    3   4      3  2   5                                                  500  0    4   5      5  3   5                                            102   250  0    5   5      4  3   4                                                  500  0    5   5      5  4   4                                            103   250  0    3   5      3  2   3                                                  500  0    4   5      5  4   5                                            104   250  0    2   5      2  4   4                                                  500  0    4   5      4  5   5                                            105   250  0    3   5      2  3   5                                                  500  0    4   5      3  4   5                                            106   250  0    4   5      2  4   5                                                  500  0    5   5      3  5   5                                            107   250  0    3   5      2  3   5                                                  500  0    5   5      3  3   5                                            108   250  0    2   5      1  2   2                                                  500  0    2   5      2  4   4                                            109   250  0    2   3      2  2   3                                                  500  0    2   5      2  4   3                                            110   250  0    2   3      3  3   4                                                  500  0    3   4      4  4   5                                            111   250  0    2   5      2  4   5                                                  500  0    2   5      3  4   5                                            112   250  0    2   5      2  4   4                                                  500  0    2   5      2  5   5                                            113   250  0    2   5      2  2   4                                                  500  0    2   5      3  3   5                                            114   250  0    2   4      2  5   5                                                  500  0    2   5      3  5   5                                            115   250  0    3   5      2  3   5                                                  500  0    4   5      3  5   5                                            116   250  0    3   5      3  3   5                                                  500  0    5   5      5  5   5                                            117   125  0    5   5      5  3   5                                                  250  0    5   5      5  4   5                                            118   250  0    2   4      2  4   5                                                  500  0    3   5      3  5   5                                            119   125  0    4   5      5  5   5                                                  250  0    5   5      5  5   5                                            120   250  0    2   4      1  4   5                                                  500  0    2   4      2  5   5                                            121   250  0    2   4      3  5   3                                                  500  0    2   5      3  5   4                                            122   250  0    2   5      3  2   3                                                  500  0    3   5      4  3   3                                            123   250  0    3   4      2  5   5                                                  500  0    3   4      4  5   5                                            124   250  0    3   4      1  3   4                                                  500  0    3   5      2  5   4                                            125   250  0    2   5      1  2   4                                                  500  0    3   5      2  3   5                                            126   250  0    2   4      1  2   3                                                  500  0    3   4      1  2   3                                            127   250  0    2   4      1  2   3                                                  500  0    2   5      1  2   4                                            128   250  0    2   4      1  3   3                                                  500  0    3   5      1  4   4                                            129   250  0    2   3      1  2   4                                                  500  0    2   4      1  3   5                                            130   250  0    2   3      2  2   4                                                  500  0    3   4      3  3   5                                            __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     Com-                                                                           pound                          NMR (60 MHz)             IR                     No.  Y  R.sup.15                                                                               R.sup.16                                                                               Properties                                                                            (δ ppm, CCl.sub.4) (cm.sup.-1)            __________________________________________________________________________     134  O     (CH.sub.2).sub.6                                                                            n.sub.D.sup.25 1.5699                                                                 1.58(8H, br, s), 3.18-3.72(4H, m),                                             4.34(2H,                 1640                                                  s), 8.48(1H, s)                                 135  O     (CH.sub.2).sub.5                                                                            n.sub.D.sup.25 1.5760                                                                 1.63(6H, br, s), 3.28-3.68(4H,                                                                          1645                                                  4.38(2H, s), 8.50(1H, s)                        137  S  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        n.sub.D.sup.25 1.6201                                                                 1.20(6H, t, J=7Hz), 3.80(4H, q,                                                                         --7Hz),                                               4.8(2H, s), 8.52(1H, s)                         138  S  i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      n.sub.D.sup.25 1.5980                                                                 1.42(12H, d, J=7Hz), 4.22-5.0(4H, m),                                                                   --56                                                  (1H, s)                                         139  S     (CH.sub.2).sub.5                                                                            n.sub.D.sup.25 1.6453                                                                 1.65(6H, br, s), 4.00(4H, br, s), 4.82(2H,                                     s),                       --                                                   8.57(1H, s)                                     140  S     (CH.sub.2).sub.6                                                                            n.sub.D.sup.25 1.6292                                                                 1.52(8H, br, s), 3.82(2H, t, J=7Hz),                                           4.11(2H,                 --                                                    t, J=7Hz), 4.84(2H, s), 8.58(1H, s)             141  O                                                                                     ##STR143##  n.sub.D.sup.25 1.5625                                                                 1.21(6H, d, J=7Hz), 1.41-1.74(6H, m), 4.32                                     4H, m), 8.48(1H, s)      1625                   142  O     CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                        Oil    3.54(8H, m), 4.35(2H, s), 8.48(1H,                                                                      1620                   143  O                                                                                     ##STR144##  Oil    2.19-2.38(7H, m), 3.40(4H, t, J=7Hz), 4.26                                     2H, s), 8.44(1H, s)      1630                   144  O                                                                                     ##STR145##  n.sub.D.sup.25 1.5659                                                                 1.16(3H, d, J=8Hz), 1.58(6H, br, s),                                           2.48-3.21 (2H, m), 3.69-4.68(3H, m),                                           8.62(1H, s)              1635                   145  O                                                                                     ##STR146##  n.sub.D.sup.25 1.5592                                                                 1.82(3H, t, J=7Hz), 1.56(6H, br, s),                                           2.76(2H, m), 3.6-4.5(5H, m), 8.5(1H,                                                                    1635                   146  O                                                                                     ##STR147##  n.sub.D.sup.25 1.5653                                                                 0.87(3H, d, J=7Hz), 1.18-2.00(5H, m),                                          2.17- 3.10(2H, m), 3.48-4.25(2H, m),                                           4.33(2H, s), 8.48(1H, s) 1640                   147  O  CH.sub.3                                                                               CH.sub.2 CH.sub.2 OH                                                                   n.sub.D.sup.25 1.5819                                                                 2.98(3H, s), 3.10-3.70(4H, m), 4.28(2H,                                        s),                      3430                                                  8.44(1H, s)              1640                   148  O  n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5248                                                                 0.48-1.80(14H, m), 2.92-3.40(4H, m),                                           4.22(2H,                 1650                                                  s), 8.38(1H, s)                                 149  O  CH.sub.2 CH.sub.2 OH                                                                   CH.sub.2 CH.sub.2 OH                                                                   n.sub.D.sup.25 1.5931                                                                 3.00-3.76(8H, m), 4.10-4.42(4H, m),                                            8.72(1H,                 3400                                                  s), (DMSO-d6)            1640                   150  O  i-C.sub.4 H.sub.9                                                                      i-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5246                                                                 1.84(6H, d, J=7Hz), 1.92(2H, h, J=7Hz),                                        3.07(4H,                 1650                                                  d, J=7Hz), 4.28(2H, s), 8.39(1H, s)             151  O  CH.sub.2 CHCH.sub.2                                                                    CH.sub. 2 CHCH.sub.2                                                                   n.sub.D.sup.25 1.5618                                                                 3.78-4.05(4H, m), 4.33(2H, s),                                                 4.82-6.10(6H,            1655                                                  m), 8.45(1H, s)                                 152  O  s-C.sub.4 H.sub.9                                                                      s-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5557                                                                 0.88(6H, t, J=7Hz), 1.25(6H, d, J=7Hz),                                        1.45-                    1655                                                  2.00(4H, m), 2.70-3.75(2H, m), 4.29(2H,                                        s),                                                                            8.42(1H, s)                                     153  O                                                                                     ##STR148##  n.sub.D.sup.25 1.5572                                                                 1.15(6H, d, J=7Hz), 2.29-2.82(2H, m),                                          2.90- 4.20(4H, m), 4.38(2H, s), 8.48(1H,                                       s)                       1660                   154  O                                                                                     ##STR149##  n.sub.D.sup.25 1.5658                                                                 0.90(2H, d, J=6Hz), 1.07-1.89(5H, m),                                          2.48- 3.10(2H, m), 3.68-4.45(4H, m),                                           8.45(1H, s)              1650                   155  O                                                                                     ##STR150##  n.sub.D.sup.25 1.5596                                                                 1.85(6H, d, J=7Hz), 1.15-2.56(6H, m),                                          2.80- 4.50(4H, m), 8.42(1H,                                                                             1660                   156  O  n-C.sub.4 H.sub.9                                                                      n-C.sub.6 H.sub.13                                                                     n.sub.D.sup.25 1.5269                                                                 0.67-1.80(18H, m), 2.92-3.47(4H, m),                                                                    1655                                                  (2H, s), 8.45(1H, s)                            157  O  C.sub.2 H.sub.5                                                                        n-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5408                                                                 0.67-1.81(10H, m), 3.32(4H, q, J=7Hz),                                         4.32                     1650                                                  (2H, s), 8.46(1H, s)                            158  O                                                                                     ##STR151##  n.sub.D.sup.25 1.5612                                                                 1.62-2.49(4H, m), 3.07-3.86(2H, m), 4.21-                                      4.72(3H, m), 8.52(1H, s), 9.96(1H, br,                                                                  3000, 1730, 1650       159  O  CH.sub.3                                                                               n-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5458                                                                 0.65-1.80(7H, m), 2.87(3H, s),                                                 3.0-3.52(2H,             1660                                                  m), 4.29(2H, s), 8.43(1H, s)                    160  O  CH.sub.3                                                                               n-C.sub.6 H.sub.13                                                                     n.sub.D.sup.25 1.5336                                                                 0.6-1.82(11H, m), 2.90(3H, s),                                                 3.02-3.48(2H,            1660                                                  m), 8.45(1H, s)                                 161  O  CH.sub.3                                                                               c-C.sub.7 H.sub.13                                                                     n.sub.D.sup.25 1.5639                                                                 1.0-2.0(12H, br, s), 2.79(3H, s),                                              3.57-4.22                1650                                                  (1H, m), 4.34(1H, s), 8.51(1H, s)               162  O  CH.sub.3                                                                               c-C.sub.6 H.sub.11                                                                     n.sub.D.sup.25 1.5687                                                                 0.84-2.00(10H, m), 2.83(3H, s),                                                                         1630-4.15                                             (1H, m), 4.32(2H, s), 8.49(1H, s)               163  O  C.sub.2 H.sub.5                                                                        c-C.sub.6 H.sub.11                                                                     n.sub.D.sup.25 1.5515                                                                 0.69-2.04(13H, m), 3.30(2H, q, J=7Hz),                                         3.60-                    1650                                                  4.16(1H, m), 4.35(2H, s), 8.48(1H, s)           164  O  n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                      n.sub.D.sup.25 1.5362                                                                 0.77(6H, t, J=7Hz), 1.48(4H, h, J=7Hz),                                        3.16                     1660                                                  (4H, t, J=7Hz), 4.23(2H, s), 8.40(1H, s)        165  O  CH.sub.3                                                                               (CH.sub.2).sub.3 OCH.sub.3                                                             n.sub.D.sup.25 1.5471                                                                 1.43-2.0(2H, m), 2.9(3H, s),                                                                            1660-3.58(7H,                                         m), 4.31(2H, s), 8.44(1H,                                                                               1120                   166  O  CH.sub.3                                                                               (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                      n.sub.D.sup.25 1.5379                                                                 1.10(3H, t, J=6H), 1.76(2H, q, J=6Hz),                                         2.91                     1665                                                  (3H, s), 3.18- 3.62(6H, m), 4.35(2H, s),                                       8.49                     1120                                                  (1H, s)                                         167  O  CH.sub.3                                                                               (CH.sub.2).sub.3 OPri                                                                  n.sub.D.sup.25 1.5245                                                                 1.05(6H, d, J=7Hz), 1.70(2H, q, J=7Hz),                                        2.90                     1660                                                  (3H, s), 3.09-3.63(7H, m), 4.30(2H, s),                                        8.41                     1080                                                  (1H, s)                                         168  O  CH.sub.3                                                                               (CH.sub.2).sub.2 OEt                                                                   n.sub.D.sup.25 1.5420                                                                 1.15(3H, t, J=7Hz), 3.02(3H, s),                                                                        1660-3.65                                             (6H, m), 4.36(2H, s), 8.48(1H,                                                                          1120                   169  O  CH.sub.3                                                                               c-C.sub.6 H.sub.9                                                                      Oil    1.0-2.1(8H, br, s), 2.77(3H, s),                                               4.1-4.8(3H,              1650                                                  m), 8.48(1H, s), (CDCl.sub.3)                   170  O  C.sub.2 H.sub.5                                                                        i-C.sub.4 H.sub.9                                                                      Oil    0.91(6H, d, J=7Hz), 1.18(3H, t, J=7Hz),                                        2.00                     1660                                                  (1H, h, J=7Hz), 3.18(2H, d, J=7Hz),                                            3.41(2H, q,                                                                    J=7Hz), 4.45(2H, s), 8.52(1H, s),                                              (CDCl.sub.3)                                    171  O  n-C.sub.3 H.sub.7                                                                      n-C.sub.4 H.sub.9                                                                      Oil    0.65-1.95(12H, m), 2.90-3.55(4H, m),                                                                    1660                                                  (2H, s), 8.49(1H, s), (CDCl.sub.3)              172  O  i-C.sub.3 H.sub.7                                                                      n-C.sub.4 H.sub.9                                                                      Oil    0.63-1.85(13H, m), 2.84-3.40(2H, m),                                                                    1650-                                                 4.5(3H, m), 8.47(1H, s), (CDCl.sub.3)           173  O  s-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5321                                                                 0.65-1.90(14H, m), 2.85-3.37(2H, m),                                                                    1650-                                                 4.21(1H, m), 4.32(2H, s), 8.47(1H, s)           174  O  n-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      n.sub.D.sup.25 1.5494                                                                 0.75-1.82(11H, m), 2.92-3.41(2H, m),                                                                    1645-                                                 4.58(3H, m), 8.51(1H, s)                        175  O  i-C.sub.3 H.sub.7                                                                      s-C.sub.4 H.sub.9                                                                      n.sub.D.sup.25 1.5332                                                                 0.80-2.40(15H, m), 3.08(2H, d, J=7Hz),                                         3.30-                    1650                                                  4.02(1H, m), 4.39(2H, s), 8.50(1H, s)           176  O  n-C.sub.3 H.sub.7                                                                      s-C.sub.4 H.sub.9                                                                      Oil    0.7-2.0(13H, m), 2.9-3.35(2H, m),                                              3.60-4.30                1650                                                  (1H, m), 4.42(2H, s), 8.50(1H, s),                                             (CDCl.sub.3)                                    177  O  CH.sub.3                                                                               i-C.sub.4 H.sub.9                                                                      Oil    0.85(6H, d, J=7Hz), 1.15-2.35(1H, m),                                          2.70-                    1660                                                  3.38(5H, m), 4.38(2H, s), 8.48(1H,              __________________________________________________________________________                                    s)                                         

                                      TABLE 4                                      __________________________________________________________________________           Amount    Herbicidal Effect                                                    of Com-                                                                             Damage                                                                              Barn-                                                                              Small Flower                                               Compound                                                                             pound                                                                               to Crop                                                                             yard-                                                                              Umbrella-                                                                             Bul-                                                                              Mono-                                                                              Broad-                                       No.   g/10a                                                                               Rice grass                                                                              plant  rush                                                                              choria                                                                             leaved                                       __________________________________________________________________________     131   250  0    5   5      4  --  4                                                  125  0    4   5      4  --  4                                            132   250  0    3   4      4  3   4                                                  125  0    2   4      3  3   4                                            133   125  0    5   5      5  5   5                                                  60   0    5   5      5  5   5                                            134   125  0    5   5      4  5   5                                                  60   0    5   5      4  5   5                                            135   250  0    3   5      3  --  4                                                  125  0    3   4      2  --  3                                            138   250  0    4   5      4  --  4                                                  125  0    3   5      3  --  4                                            139   250  0    4   5      2  --  5                                                  125  0    3   5      2  --  4                                            140   250  0    3   5      2  --  4                                                  125  0    3   5      2  --  4                                            141   125  0    5   5      3  5   5                                                  60   0    5   5      3  4   5                                            144   60   0    5   5      4  3   4                                                  30   0    5   5      3  3   4                                            145   125  0    5   5      5  5   5                                                  60   0    5   5      5  5   5                                            146   250  0    4   5      4  4   4                                                  125  0    3   5      3  3   4                                            148   125  0    5   5      5  4   4                                                  60   0    5   5      4  3   4                                            150   250  0    5   5      4  5   4                                                  125  0    5   5      4  4   4                                            151   250  0    5   5      4  5   5                                                  125  0    3   4      3  5   4                                            152   250  0    5   4      4  4   3                                                  125  0    5   4      3  2   2                                            157   125  0    5   5      5  5   5                                                  60   0    5   5      5  5   5                                            159   125  0    5   5      5  4   5                                                  60   0    5   5      5  3   5                                            160   250  0    5   5      5  5   5                                                  125  0    5   5      5  4   5                                            161   250  0    5   5      5  5   5                                                  125  0    5   5      4  5   5                                            162   250  0    5   5      5  5   5                                                  125  0    5   5      5  5   5                                            163   250  0    5   5      5  5   5                                                  125  0    5   5      5  5   5                                            164   125  0    5   5      5  5   5                                                  60   0    5   5      4  4   4                                            170   250  0    5   5      5  5   5                                                  125  0    4   5      4  5   5                                            171   250  0    5   5      5  5   5                                                  125  0    5   5      5  5   5                                            172   250  0    5   5      5  5   5                                                  125  0    5   5      5  5   5                                            173   125  0    5   5      5  4   5                                                  60   0    3   5      5  2   5                                            174   250  0    5   5      5  5   5                                                  125  0    5   5      5  5   5                                            175   125  0    5   4      5  4   4                                                  60   0    5   4      4  4   4                                            176   125  0    5   5      5  5   4                                                  60   0    5   5      5  3   4                                            177   125  0    5   5      5  5   5                                                  60   0    5   5      5  5   5                                            __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________           Amount    Herbicidal Effect                                                    of Com-                                                                             Damage                                                                              Barn-                                                                              Small Flower                                               Compound                                                                             pound                                                                               to Crop                                                                             yard-                                                                              Umbrella-                                                                             Bul-                                                                              Mono-                                                                              Broad-                                       No.   g/10a                                                                               Rice grass                                                                              plant  rush                                                                              choria                                                                             leaved                                       __________________________________________________________________________     178   30   0    5   5      5  5   5                                                  15   0    5   5      5  5   5                                            179   30   0    5   5      5  5   5                                                  15   0    5   5      5  5   5                                            180   30   0    5   5      5  5   5                                                  15   0    5   5      5  5   5                                            181   30   0    5   5      5  5   5                                                  15   0    5   5      5  5   5                                            182   30   0    5   5      5  5   5                                                  15   0    5   5      5  5   5                                            __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________           Amount    Herbicidal Effect                                                    of Com-                                                                             Damage                                                                              Barn-                                                                              Small Flower                                               Compound                                                                             pound                                                                               to Crop                                                                             yard-                                                                              Umbrella-                                                                             Bul-                                                                              Mono-                                                                              Broad-                                       No.   g/10a                                                                               Rice grass                                                                              plant  rush                                                                              choria                                                                             leaved                                       __________________________________________________________________________     183   125  0    4   5      5  5   5                                                  250  0    5   5      5  5   5                                            184   250  0    4   5      5  5   5                                                  500  0    5   5      5  5   5                                            185   125  0    3   5      5  3   5                                                  250  0    4   5      5  4   5                                            186   250  0    4   5      5  4   5                                                  500  0    5   5      5  4   5                                            187   250  0    4   3      5  3   5                                                  500  0    5   5      5  4   5                                            188   250  0    4   5      4  4   5                                                  500  0    5   5      5  4   5                                            __________________________________________________________________________ 

We claim:
 1. A thiadiazole compound of the formula: ##STR152## wherein X, V and Z, which may be the same or different, each represent hydrogen, halogen, C₁ -C₄ alkyl, C₁₋₄ haloalkyl, C₁ -C₄ alkoxy, hydroxy or nitro, with the proviso that two or three of them cannot simultaneously be hydrogen; A represents hydrogen atom, allyl or propargyl.
 2. The thiadiazole compound according to claim 1, wherein A represents hydrogen atom.
 3. A thiadiazole compound of the formula: ##STR153## wherein X, V and Z, the same or different, represent hydrogen, halogen, C₁₋₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, hydroxy or nitro, with the proviso that two or three of X, V and Z cannot simultaneously be hydrogen; A represents --SO₂ R¹ (wherein R¹ represents C₁ -C₄ alkyl which may be substituted with halogen; a phenyl group which may be substituted with C₁ -C₄ alkyl; or an amino group which is substituted with C₁ -C₄ alkyl); --CHR⁷ COR⁸ (wherein R⁷ represents a hydrogen atom or C₁ -C₄ alkyl, R⁸ represents a hydroxy group or amino group which may be substituted with a C₁ -C₄ alkyl group, a phenyl group or both); --C(═W)OR⁹ (wherein W represents an oxygen atom or a sulfur atom, R⁹ represents C₁ -C₄ alkyl which may be substituted with halogen, (C₁ -C₄) alkoxy (C₁ - C₄) alkyl, benzyl, phenyl, tetrahydrofurfuryl or alkylideneamino group); or --COR¹⁰ (wherein R¹⁰ represents phenyl, C₁ -C₄ alkyl, or C₃ -C₆ cycloalkyl which may be substituted with halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, nitro or with cyano group.
 4. The thiadiazole compound according to claim 3, wherein A represents --SO₂ R¹ (R¹ represents C₁ -C₄ alkyl which may be substituted with halogen; a phenyl group which may be substituted with C₁ -C₄ alkyl, or amino group which is substituted with C₁ -C₄ alkyl); or --CHR⁷ COR⁸ (wherein R⁷ represents a hydrogen atom or C₁ -C₄ alkyl, and R⁸ represents a hydroxy group or amino group which may be substituted with C₁ -C₄ alkyl group and/or with phenyl group).
 5. A herbicidal composition comprising as an effective ingredient the thiadiazole compound according to claim 1 together with an agriculturally acceptable carrier.
 6. A herbicidal composition comprising as an effective ingredient the thiadiazole compound according to claim 2 together with an agriculturally acceptable carrier.
 7. A herbicidal composition comprising as an effective ingredient the thiadiazole compound according to claim 3 together with an agriculturally acceptable carrier.
 8. A herbicidal composition comprising as an effective ingredient the thiadiazole compound according to claim 4 together with an agriculturally acceptable carrier. 